Review

Orange Peel Waste as a Source of Bioactive Compounds and

Valuable Products: Insights Based on Chemical Composition
and Biorefining
Mariana Ortiz-Sanchez * , Carlos Ariel Cardona Alzate and Juan Camilo Solarte-Toro

Departamento de Ingeniería Química, Instituto de Biotecnología y Agroindustria, Universidad Nacional de

Colombia Sede Manizales, Manizales 170003, Colombia; [email protected] (C.A.C.A.);
[email protected] (J.C.S.-T.)
* Correspondence: [email protected]

Abstract: Few valorization pathways have been implemented as alternatives to reduce the orange
peel waste (OPW) disposal in landfills. OPW can be a source of income or economic savings in juice
production factories since this waste is a potential source of value-added products (e.g., bioactive com-
pounds) and energy vectors (e.g., biogas). Valorization alternatives should be based on (i) orange peel
chemical composition, (ii) market analysis, and (iii) availability. Nevertheless, few literature papers
have highlighted the chemical composition change caused by the different juice production schemes
as a potential opportunity to obtain different value-added products and biorefinery schemes. Thus,
the aims of this review paper are related to (i) reviewing different orange fruit processing pathways,
(ii) analyzing several OPW chemical compositions reported in the open literature, (iii) providing a
summary of OPW extraction pathways for bioactive compounds production, and (iv) evaluating
the effect of applying different extraction methods on bioactive compound extraction performance.
This review includes a description of the OPW matrix, market insights, packaging, physicochemical
characterization, processing technologies, and suggested biorefinery approaches. Finally, different
Citation: Ortiz-Sanchez, M.; Cardona
extraction methods for obtaining bioactive compounds from OPW are compared. As a result, the
Alzate, C.A.; Solarte-Toro, J.C. Orange
supercritical fluid extraction process has the highest extraction performance and selectivity since this
Peel Waste as a Source of Bioactive
method extracted a high amount of hesperidin (8.18 g/kg OPW db.). In conclusion, OPW is a source
Compounds and Valuable Products:
of bioactive compounds and valuable products that can be introduced in juice-producing factories to
Insights Based on Chemical
Composition and Biorefining. Biomass
increase product portfolio or economic savings by changing the energy matrix.
2024, 4, 107–131. https://doi.org/
10.3390/biomass4010006 Keywords: bioactive compounds; biorefineries; chemical composition analysis; extraction technologies;
orange peel waste valorization; orange processing
Academic Editors: Vassilis
Athanasiadis, Theodoros G.
Chatzimitakos, Dimitris P. Makris
and Lasse Rosendahl
1. Introduction
Received: 23 June 2023 Orange is one of the most popular citrus crops in the world. This fruit has sev-
Revised: 26 October 2023
eral healthy compounds such as vitamin C, folic acid, antioxidants, flavonoids, and cate-
Accepted: 2 January 2024
chins [1,2]. The orange crop has been considered a versatile crop because this fruit can be
Published: 2 February 2024
produced in different soils and climatic conditions [3]. Several countries between 30◦ –35◦
north and south of Ecuador can produce oranges. Citrus sinensis (L.) Osbeck is the most
important species of sweet orange in the world. Seminara et al. [3] reported four orange
Copyright: © 2024 by the authors.
classifications according to the orange color. Hence, sweet oranges can be classified as com-
Licensee MDPI, Basel, Switzerland. mon, navel, blood, and acidless. Common oranges are the most produced and consumed
This article is an open access article worldwide. Indeed, the common orange group can be subdivided into different types, such
distributed under the terms and as Salustiana, Valencia Midknight, Valencia Barberina, Ovale, Valencia Late, Valencia Delta,
conditions of the Creative Commons and Ruby Valencia. All of these cultivars are suitable for industrial processing because these
Attribution (CC BY) license (https:// varieties have a high juice yield and low content of bittering compounds. However, Valen-
creativecommons.org/licenses/by/ cia oranges are the most used fruits as raw material for juice, jams, and pulp production
4.0/). due to the adaptability of this variety to different climatic conditions. The most important

Biomass 2024, 4, 107–131. https://doi.org/10.3390/biomass4010006 https://www.mdpi.com/journal/biomass

 compounds. However, Valencia oranges are the most used fruits as raw material for
jams, and pulp production due to the adaptability of this variety to different climatic
ditions. The most important orange exporters in the world are Spain, Egypt, Greece,
rocco, Netherlands, Italy, The United States of America (USA), Argentina, Brazil, C
Biomass 2024, 4 108
Uruguay, Honduras, Mexico, Colombia, China, and Zimbabwe. Meanwhile, the mos
portant countries for orange processing are the USA, Mexico, Brazil, China, Spain, Ar
tina, Greece,
orange and Italy
exporters in the [4].
world are Spain, Egypt, Greece, Morocco, Netherlands, Italy, The
United States ofvarieties
All orange America (USA),
have aArgentina, Brazil, Chile, Uruguay,
similar morphology. Honduras,
Nevertheless, thisMexico,
fruit has a d
Colombia, China, and Zimbabwe. Meanwhile, the most important countries for orange
ent chemical composition and physical characteristics depending on the variety,
processing are the USA, Mexico, Brazil, China, Spain, Argentina, Greece, and Italy [4].
stock, soil, fertilization,
All orange irrigation,
varieties have a similar age, maturity,
morphology. and position
Nevertheless, inhas
this fruit thea tree [5,6]. Ora
different
diameter
chemicalranges fromand
composition 4 to 12 cmcharacteristics
physical [7]. The fruit size depends
depending on the
on the variety, variety,soil,
rootstock, growing
ditions, and maturation.
fertilization, irrigation, age, This fruit and
maturity, comprises
position eight different
in the tree tissues and
[5,6]. Oranges’ the seed [7
diameter
ranges from 4 to 12 cm [7]. The fruit size depends on the variety,
general, the weight of oranges is 87% water and 13% compounds such as minerals, e growing conditions, and
maturation. This fruit comprises eight different tissues and the seed [7]. In general, the
tialweight
oils, fats, proteins, fibers, organic acids (e.g., formic acid and citric acid), pectin,
of oranges is 87% water and 13% compounds such as minerals, essential oils, fats,
cosides, and pentosans
proteins, fibers, organic acids [8]. These compounds
(e.g., formic are distributed
acid and citric acid), pectin, in the eightand
glucosides, tissues o
orange. On [8].
pentosans the These
othercompounds
hand, oranges are consumed
are distributed as atissues
in the eight freshofproduct andOnjuice.
the orange. the The e
other hand, oranges are consumed as a fresh product and juice. The edible
fraction of the fruit involves the segments and juice sacs (pulp or rag). The edible fra fraction of the
fruit involves the segments and juice sacs (pulp or rag). The edible fraction is about 31–51%
is about 31–51% of total fruit weight. Instead, the non-edible fraction is the cuticl
of total fruit weight. Instead, the non-edible fraction is the cuticle, oil glands, flavedo, core,
glands,
segment flavedo,
membranes,core,and segment membranes,
albedo. The and albedo.
non-edible fraction The tonon-edible
corresponds fraction c
49–69% of total
sponds to 49–69%
fruit weight of totalthe
[7]. Moreover, fruit weightfraction
non-edible [7]. Moreover, the non-edible
is called orange fraction
peel waste (OPW) [9].is calle
ange peel1 shows
Figure wastean (OPW)
outline[9]. Figure
of the 1 shows
morphology anorange.
of an outline of the morphology of an orang

Segments
Juice Sacs

Core

Flavedo Segment
Membranes
Oil Glands

Albedo

Figure 1. 1.Orange
Figure Orange fruit constituents.
fruit constituents.

Oranges have been used to produce several food products (e.g., juice) at the industrial
Oranges have been used to produce several food products (e.g., juice) at the in
level [10]. Thus, large amounts of OPW are produced worldwide without a specific
trial level [10].
treatment Thus, large
or valorization amounts
route (i.e., 24 of OPWtons
million areofproduced
OPW) [11].worldwide
Currently, OPW without
is a sp
treatment or valorization route (i.e., 24 million tons of OPW) [11]. Currently, OPW is
disposed of in landfills producing large amounts of greenhouse gas emissions and leachates
with of
posed a high chemical oxygen
in landfills producingdemand.
largeThus, innovative
amounts ofways to use andgas
greenhouse valorize this waste
emissions and leac
have been studied to mitigate OPW environmental damage and promote the sustainability
with a high chemical oxygen demand. Thus, innovative ways to use and valorize
of the citrus value chain at regional, national, and worldwide levels. This statement is true
waste
sincehave beenOPW
upgrading studied to mitigate
to bio-based productsOPW environmental
reduces damage
the environmental impactand promote
caused by the
tainability of the
the poor peel citrus value
disposition chain
and the at regional,
replacement national,
of oil-based and[12].
products worldwide levels. This s
OPW has different chemical compositions depending
ment is true since upgrading OPW to bio-based products reduces on the juice extraction process
the environmenta
pact caused by the poor peel disposition and the replacement of oil-basedcom-
(manual or industrial). Cellulose, hemicellulose, and pectin are the most important products [
ponents. Several authors have reported different ways to upgrade and obtain different
OPW has different chemical compositions depending on the
value-added products and extract bioactive compounds in stand-alone processes and biore-
juice extraction pr
(manual or industrial).
finery configurations Cellulose,
[13–15]. Higher hemicellulose,
yields have been and pectinbyare
reported the most
applying important
different
ponents. Several
extraction methods authors have reported
such as solvent extraction, different ways toextraction,
ultrasound-assisted upgrademicrowave-
and obtain diff
value-added products and extract bioactive compounds in stand-alonereports
assisted extraction, and supercritical fluids [16–19]. Nevertheless, few literature processes an
have analyzed the possible influence of the OPW chemical composition on obtaining high
orefinery configurations [13–15]. Higher yields have been reported by applying diff
extraction yields. Moreover, few literature papers have highlighted the influence of the juice
extraction
extractionmethods
method onsuch as solvent
the OPW chemicalextraction,
compositionultrasound-assisted
On the other hand, a global extraction,
summary microw
assisted
relatedextraction, and supercritical
to the valorization possibilities of fluids
obtaining[16–19]. Nevertheless,
bioactive few literature re
compounds, value-added
have analyzed the possible influence of the OPW chemical composition on obtaining
extraction yields. Moreover, few literature papers have highlighted the influence o
juice extraction method on the OPW chemical composition On the other hand, a g
Biomass 2024, 4 109

products, and energy vectors is required before proposing OPW upgrading pathways. For
these reasons, the aims of this review paper are related to (i) reviewing different orange
fruit processing pathways, (ii) analyzing several OPW chemical compositions reported in
the open literature, (iii) providing a summary of OPW extraction pathways for bioactive
compounds production, and (iv) evaluating the effect of applying different extraction
methods on the bioactive compounds extraction performance. In addition, this review
includes a description of the OPW matrix, market insights, packaging, physicochemical
characterization, processing technologies, and suggested biorefinery approaches.

2. Orange Fruit Processing and OPW Origin

Oranges are commercialized as fresh fruit or juice [20]. Traditional orange marketing
does not comply with technical standards in most producing areas [21]. Direct orange
commercialization has a high participation of intermediaries in the orange value chain.
Thus, the price per unit of orange increases until the final consumer. Traditional marketing
has been denominated as primary processing, since oranges do not have a direct trans-
formation [21]. On the other hand, juice production is the industrial commercialization
way (so-called secondary processing) [22]. In this case, the industry directly purchases
oranges from the producers (e.g., farmers or first-level organizations), decreasing the price
per unit of the fruit. This orange commercialization pathway evidences more incomes for
farmers since the traditional pathway dilutes the intermediaries’ incomes. Moreover, juice
production creates a specialized market with a greater demand for quality and size. Two
modes are presented under this type of distribution [23]. The first mode is purchasing the
fruit from the producer (industry only). The second mode is when the fruit producer also
performs the processing (industrial orchard) [23]. The objective of the second mode is to
maximize the crop proportion marketed as fresh fruit, processing only the fruit that cannot
be sold due to external quality, fruit size, trade barriers, or excess production. In primary
or secondary processing, fruit selection is needed. Then, the packing operations are an
essential link in the citrus production, processing, and commercialization [24]. The stacked
fruit for storage and transport is distributed according to weight. A standard packaged box
corresponds to 90 lb (approximately 41 kg) [20]. Figure 2 presents the simplified flowchart
of orange processing.
The orange processing industry generates different types of products and by-products.
The most known orange-based products are juice, jellies, marmalades, and essential oils [25,26].
Since 1980, about 30% of the oranges grown worldwide have been processed [27]. Orange
juice is considered the most significant product. After packing house operations (industrial
orchard) or harvesting for industry, oranges are conveyed to the processing plant. In
countries like the USA, Brazil, and China, the packing house operations are not considered
because the processing plant is near the crop [24]. In contrast, countries such as Argentina
and Colombia must include the packing and transport stages [10]. The next step is to deliver
the oranges to the processing facility. Then, the fruits are washed (with 200 ppm of chlorine)
and revised to identify low-quality fruits [21]. The juice extraction process is carried out
after washing. This step is the “heart” of the juice production process. Orange juice is
obtained by mechanical extraction. Juice extraction seeks to obtain as much juice as possible
from the fruit, avoiding albedo and oil in the juice. These impurities can cause bitterness in
the juice flavor and decrease product quality [22,28]. Thus, orange juice extraction is the key
to defining product quality. Different equipment has been designed for producing orange
juice, since the efficiency of the process means more income [28]. Essential oil extraction is
mandatory, no matter the orange juice equipment. Nevertheless, some industries do not
consider this step, adding fractions of essential oil to their products. Figure 3 shows the
commercial schemes for extracting the juice and essential oil from oranges.
Biomass 2024, 4 Biomass 2024, 4, FOR PEER REVIEW 110
Biomass 2024, 4, FOR PEER REVIEW 4

Figure
Figure 2. Simplified 2. Simplified
flowchart flowchart
of orange of orange processing.
processing.
Figure 2. Simplified flowchart of orange processing.

Figure 3. Commercial orange juice and essential oil extraction systems. * For example, the Fratell
Indelicato technology. ** For example, well-known in industry, the JBT (John Bean Technologi
Figure 3.
Figure 3. Commercial
Commercial orange
orange juice
juiceand
andessential
essentialoiloil
extraction systems.
extraction * For
systems. example,
* For the Fratellini
example, the Fratellini
FoodTech
Indelicato technology. FMC
** For (Food
example, Machinery
well-knownCorporation)
in industry, system.
the JBT (John Bean Technologies)
Indelicato technology. ** For example, well-known in industry, the JBT (John Bean Technologies)
FoodTech FMC (Food Machinery Corporation) system.
FoodTech FMC (Food Machinery Corporation) system.
 Orange juice extractors can be classified into different types. The rotative press ex-
Biomass 2024, 4 tractor, the squeezer, and the reamer type are the most used extractors in orange 111 pro-
cessing plants [22,28]. Table 1 shows the advantages and disadvantages of these types of
extraction equipment. Different outlet streams are obtained according to the extractor
Orange juice extractors can be classified into different types. The rotative press extrac-
model. Each stream is upgraded (valorized or treated) in a specific processing line in the
tor, the squeezer, and the reamer type are the most used extractors in orange processing
orange agro-industry (see Figure 3). These extractor models with oil removal produce a
plants [22,28]. Table 1 shows the advantages and disadvantages of these types of extrac-
diluted oil stream.Different
tion equipment. This stream
outletmust be sent
streams to an equipment
are obtained accordingseries
to the to concentrate
extractor model.the oil
[29].
Each stream is upgraded (valorized or treated) in a specific processing line in the orange
agro-industry (see Figure 3). These extractor models with oil removal produce a diluted oil
Table 1. Extraction
stream. equipment:
This stream must be advantages and disadvantages
sent to an equipment [22,28].
series to concentrate the oil [29].

Feature RotativeTablePress1.Extractor
Extraction equipment:Squeezer-Type Extractor [22,28]. Reamer-Type Extractor
advantages and disadvantages
Juice, oil emulsion, core (rag, Juice (pulp, seeds, and rag) and
Outlet streams
Feature Juice and peel.
Rotative Press Extractor Squeezer-Type Extractor Reamer-Type Extractor
seeds, and pulp), and peel. peel.
Juice, oil emulsion, core (rag, The extractor
Outlet streams and rag)gives higher qual-
TheJuice and peel.
extractor has less investment seeds,The extractor
and pulp),
Juice (pulp,
provides excellent
and peel.
seeds, and peel.
Advantages ity pulp (longer and larger cell
andThe
hasextractor
greaterhascapacity
less per unit. juice, oil, and peel separation.
Advantages investment and has greater
The extractor provides excellent fragments).
The extractor gives higher quality pulp
juice, oil, and peel separation. (longer and larger cell fragments).
capacity per unit. The extractor damages the peel The extractor requires two sepa-
The extractor has the lowest yield
Disadvantages and generates
The extractor damages thea diluted
peel oil ration
The extractor steps
requires twotoseparation
extract juice and
Disadvantages
andThe
juice quality.
extractor has the lowest
and generates a diluted steps to extract juice and oil from
yield and juice quality. emulsion. oil from the fruit.
oil emulsion. the fruit.
Capacity 1500 L/h 2500 L/h 2500 L/h
Capacity 1500 L/h 2500 L/h 2500 L/h

Three pathways for industrial orange processing have been elucidated based on the
Three pathways
juice extraction model.for industrial
The orange processing
three industrial have been elucidated
orange processing pathwaysbased on the
involve some or
juice extraction model. The three industrial orange processing pathways
all of the outlet streams presented in Figure 3. The first orange processing pathway involve some or has
all of the outlet streams presented in Figure 3. The first orange processing pathway
the lowest complexity at the industrial level (see Figure 4). The first processing pathway has the
lowest complexity at the industrial level (see Figure 4). The first processing pathway aims
aims to produce only orange juice, leaving aside the possible upgrading of other com-
to produce only orange juice, leaving aside the possible upgrading of other compounds
pounds
presentpresent in the
in the fruit. fruit.
The The resulting
resulting juice
juice in this in this
process hasprocess has
essential oilessential oil traces, de-
traces, decreasing
creasing
the juicethequality.
juice quality. This processing
This processing line hasline has
been been implemented
implemented in small-scale
in small-scale facilities, facil-
ities, producing
producing largelarge amounts
amounts of OPW ofwith
OPW withconcentration
a high a high concentration
of essential of
oil,essential oil, fiber,
fiber, protein,
protein, and [23].
and pectin pectin [23].

Figure
Figure4.4.First
Firstpathway forindustrial
pathway for industrial orange
orange processing:
processing: low complexity—only
low complexity—only orange juiceorange juice pro-
production.
duction.
The second orange processing pathway involves an additional processing line com-
pared to the first pathway. Thus, this pathway has a medium complexity level since orange
The second orange processing pathway involves an additional processing line com-
juice and essential oil are produced simultaneously. The juice quality is better than in the
pared to the first pathway. Thus, this pathway has a medium complexity level since or-
case of the first pathway since essential oil traces are not present in the juice. The OPW
ange juice and
produced essential
in this processoil are
has produced
a lower simultaneously.
content of essential oil. The juice
Thus, quality
lower yieldsiswill
better
be than
in obtained
the case ifofsome
the first pathway
experiments aresince
carriedessential oil traces are
out. Nevertheless, thisnot
OPW present in the
can have juice. The
a higher
OPWbiogas production potential since limonene (the most important compound in essential oil) will
produced in this process has a lower content of essential oil. Thus, lower yields
behas
obtained if some experiments
been considered an inhibitor in are carried
this out.
process. Nevertheless,
Figure thisblock
5 presents the OPW can have
diagram a higher
of the
second
biogas orange processing
production potentialpathway
since [23].
limonene (the most important compound in essential
oil) has been considered an inhibitor in this process. Figure 5 presents the block diagram
of the second orange processing pathway [23].
 Biomass
s 2024, 4, FOR PEER
Biomass 2024, 44, FOR PEER REVIEW
REVIEW
2024, 6 1126

Figure
Figure 5. SecondFigure 5. Second
pathway
5. Second pathway
for industrial
pathway for industrial
orange
for industrial orange
processing: processing:
medium
orange medium complexity—orange
complexity—orange
complexity—orange
processing: medium juice and juice and
juice and
essential oil production.
essential oil production.
essential oil production.

Theprocessing
The third orange
The thirdorange
third orange processing
method involves
processing method
method three involves three
lines (i.e.,
involves threeorangelines
lines (i.e.,
juice,
(i.e., orange
essential
orange juice,
juice, essential
essential oil,
oil, and
oil, and peel juice).
and peel peel
This juice).
process
juice). This process
Thisconfiguration
process configuration
has
configurationbeenhas hasdefined
defined
been asbeen
thedefined
most as thesustainable
as thesustainable
most most sustainable
orange
orange
orange processing processing
configuration
processing configuration
since
configuration oranges since
are
since orangesusedoranges
as much
are usedareas
used
as as much
possible.
much as possible.
Nevertheless,
as possible. Nevertheless,
Nevertheless, this
this process
this process configuration configuration
is common
process configuration is in is common
large-scale
common in large-scale
processesprocesses
in large-scale processes
since the capital since
since the and the capital
opera-
capital and opera-
and operational
tionalare
tional expenditures expenditures
are the are
the highest
expenditures the processing
of the
highest highest of the processing
lines
of the processing mentioned lines mentioned
above.
lines mentioned 6above.
FigureFigure
above. pre- 6Figure 6 pre-
presents the
sents
sents the blockblock the block
diagram
diagram diagram
of
of this of this
this industrial
industrial industrial
process
process process [23].
[23]. [23].

Figure 6. for
Figure 6. Third Figure
pathway Third pathway
industrial for industrial
orange orange
processing: processing:
highprocessing: high complexity—orange
complexity—orange juice, essential
juice, essential juice,
6. Third pathway for industrial orange high complexity—orange essential
oil,production.
oil, and peel juice and peel juice production.
oil, and peel juice production.

The orange juice Theproduction

The orange juice
orange juice production
line line includes
includes filtration,
production line includes filtration,cooling,
clarification,
filtration, clarification,
and juice
clarification, cooling, and
cooling, and juice
juice
concentration
concentration concentration
[30]. Orange juice [30].comes
[30]. Orange
Orange juice
out with
juice comes
20–25%
comes outpulp.
out with 20–25%
with 20–25%
The pulp.
firstpulp.
stageThe The
of the first
first stage of
juice
stage of the
the juice
juice
line
line consists ofline consistsabout
removing
consists removing
50% of the
of removing about
about 50%
pulp.
50% Forof this,
of the pulp.
the pulp.
the juice For is pumped
this, juice
the juice is pumped
through
is pumped
a through aa
through
finisher,
finisher, wherefinisher, where solid
solid particles
where solid particles are
are separated
particles are separated
from separated
the juice.fromfrom
On the theother
the juice.hand,
juice. On the
On the
the other hand,
juicehand,
other is the juice
the juice is
is
clarifiedby
clarified for finishing
clarified forremoving
for finishingby
finishing by
seed removing
fragments,
removing seedseed fragments,
filaments
fragments, of filaments
the
filaments ofcore
coreofmaterial,
the the material,
core
and material, and
and other
other
other undesirable undesirable
high-density
undesirable high-density
materials.
high-density Then, materials.
materials. the juicethe
Then, Then,
mustjuicethe juicebemust
bemust
pasteurized beand
pasteurized pasteurized
cooled and to
and cooled 4 ◦C
cooled
to minimize
to
to 4 °C to minimize 4 °C to minimize
possiblepossible
microbial possible
microbial microbial
activity.activity.
The juice activity.
Thecan juice The
be can juice can
be labeled
labeled beas labeled
as original original as or
or con- original or con-
concentrated.
centrated.
centrated. TheThe original
original The
juice isoriginal
juice is fresh
fresh juice
and and
hasis
hasfresh
not andconcentrated.
notbeen
been has not been The
concentrated. concentrated.
Theoriginal
original juice The isoriginal
juice juice is
more popular
moreconcentrated
more popular than popular thanjuice concentrated
juice due to
due itsjuice
toits image
image due asto
as its image
aahealthy
healthy as good
and
and a good
healthy and
flavor
flavor good flavor
product
prod- [30].prod-
The
concentrated
uct [30]. The concentrated juice
uct [30]. Thejuice isis diluted
concentrated dilutedjuice
withiswater
with diluted until reaching
with water the
reaching therequired
until reaching
required Brix
thedegrees
Brix (◦ Bx)
required
de- tode-
Brix be
sold.
grees Original
(°Bx) to juice
be sold.is often more
Original expensive
juice is often than
more concentrated.
grees (°Bx) to be sold. Original juice is often more expensive than concentrated. After ex- expensive After
than extraction,
concentrated. the juice
After is
ex-
pasteurized.
traction,
traction, the juice Finally, the
the juice isFinally,
is pasteurized. final
pasteurized. product
the final is
Finally,
productstored in
theisfinal refrigeration
stored product tanks [23].
is stored intanks
in refrigeration refrigeration tanks
[23]. [23]. The juice concentration stage is the most energy-demanding process in the orange
processing system. Nevertheless, other alternatives for this process have been researched,
Biomass 2024, 4 113

since the concentration stage decreases the antioxidant activity of the final product (i.e.,
degradation of ascorbic acid, anthocyanins, hydroxycinnamic acid, and flavonoids) [31,32].
For instance, juice concentration using membranes has been reported with relevant re-
sults [33]. Ultrafiltration has been used as a promising technology for removing impurities
and concentrating the juice. This technology reduces the degradation of antioxidant com-
pounds in juice by about 58% compared to thermal concentration [28]. Cryoconcentration
is another alternative for the concentration of orange juice. This technique consists of
juice cooling until reaching solid–liquid equilibria [28]. This step produces high-purity ice
crystals. Then, water removal is carried out with the removal of the crystals [34]. Based
on this concentration technique, the loss of aroma due to volatility or steam snatching is
almost invisible. Despite the benefits in terms of quality, this technique has high investment
costs, high energy consumption, and reaches a lower concentration (50 ◦ Brix) [35].
On the other hand, the essential oil line comprises the separation and purification of
the oil resulting from the extraction process (see, Figure 2) [36]. The resulting emulsion
contains fruit substances—including peel, pulp particles, soluble pectin, and sugars. The
essential oil extraction process comprises four steps (i.e., finishing, centrifugation, polishing,
and traces removal). The first step is to pass the emulsion through a finisher unit to remove
large shell pieces. The filtered emulsion contains approximately 0.5 to 2% of oil. The second
step is to centrifuge the emulsion to concentrate the oil to 70 or 90% by weight. In this step,
a three-phase centrifuge is used to obtain three streams (concentrated oil emulsion is the
light phase, the heavy phase is the particulate matter, and the medium phase is water). The
third step corresponds to polishing the oil in a second centrifuge. In this step, the oil is
concentrated to more than 99% by weight. Finally, the oil goes through a winterization
process. This process involves removing traces of wax dissolved in the oil. At temperatures
of 1 ◦ C or less, the waxes precipitate and sediment [37]. This step usually takes 30 days.
Subsequently, the oil is decanted and packaged.
Finally, the orange peel processing line is upgraded to utilize the highest amount of
the fruit. Then, most waste produced after orange processing is generated in this line. The
most representative residue is known as OPW [38]. OPW is composed of the membrane
residues resulting from juice extraction, seeds, and peel [39]. Different ways to upgrade
OPW at the industrial level have been reported [40–42]. Some of the alternatives to take
advantage of the side streams obtained are described.
Juice line waste: The pulp is the main waste obtained in this line. This residue is
traded as “cells.” Usually, this subproduct is used in juice drinks to provide a natural
appearance to the product [22].
Peel line waste: OPW is the most important waste produced in orange processing.
Indeed, this residue is a problem in the citrus industry since the chemical composition is
complex compared to other agro-industrial residues such as peels and seeds. The most
important factor related to OPW complexity is the high moisture content (i.e., 80%), which
encourages rotting and fungi issues in the plant (i.e., OPW is considered a source of
cross-contamination). Therefore, OPW management is key in orange processing facilities
beyond finding new valorization alternatives. One common way for OPW disposal is to
sell this waste without further treatment to nearby farmers for directly feeding ruminants
or silage [43,44]. However, stabilizing the peels by drying them is often necessary because
there will not always be a constant demand for fresh pulp feed near the processing plant.
Another alternative is to extract the pectin present in OPW. This allows us to obtain juice rich
in gelling compounds with potential applications in the food and pharmaceutical industry.
Oil line waste: This waste can be used to produce essences, which correspond to the
volatile components recovered during the oil concentration process (see, Figure 2). This by-
product can be obtained from the first centrifugation stage (aqueous phase). Water-soluble
components such as essence aroma can be added to the concentrated product or juice [37].
The abovementioned orange juice production pathways are applied by different
companies worldwide. Information to match a company with the current orange juice
production line is difficult since primary data are required. Nevertheless, the most impor-
Biomass 2024, 4 114

tant players related to the orange juice market are Astral Foods, Bar-S Foods, Campofrio
Food Group, Cargill, and The Kraft Heinz Company, among others. These multinational
companies are the leading orange juice producers today [20].

3. OPW Characterization and Potential Upgrading Routes

Several residues after orange fruit processing are produced. OPW is the most repre-
sentative fraction [11]. This section presents an overview of the OPW chemical composition
reported in the open literature. Chemical characterization refers to different compounds
present in the matrix of the residue. The most important OPW components are pectin,
cellulose, hemicellulose, lignin, protein, and fats. Nevertheless, components such as soluble
sugars, terpenes, and phenolic compounds can be found [45]. Several ways for reporting
the OPW composition have been published. For instance, Sanchez-Orozco [46] reported
OPW characterization in terms of cellulose, hemicellulose, protein, and lignin, giving values
of 11.93%, 14.46%, 5.97%, and 2.17% on a dry basis. Alvarez et al. [47] reported the cellulose,
hemicellulose, pectin, and lignin mass fractions of OPW as 17.1%, 16.6%, 35.3%, and 28.7%,
respectively. In the same way, different OPW chemical composition reports can be found
in the open literature. Table 2 summarizes the OPW chemical compositions reported in
the literature.

Table 2. OPW chemical characterization reported in the open literature (% wt., dry basis).

Sanchez- Álvarez et al. Mohsin et al. Ahmed et al. Rivas-Cantú Ortiz-Sanchez

Item
Orozco [46] [47] [48] [49] et al. [37] ** et al. [41]
Cellulose 11.93 17.10 34.53 17.52 33.98 30.17
Hemicellulose 14.46 16.60 11.38 N.R 9.99 9.35
Lignin 2.17 28.70 * 7.20 14.38 6.93 5.07
Pectin N.R. 35.30 15.28 15.72 20.90 11.18
Protein 5.97 N.R. 7.80 N.R. 9.00 4.83
Fat N.R. N.R. 3.63 4.15 3.85 5.18
Ash N.R. 2.30 2.81 16.59 2.46 3.61
Total sugars N.R. N.R. N.R. 31.62 9.00 N.R.
Flavonoids N.R. N.R. N.R. N.R. 4.00 N.R.
Total
N.R. N.R. N.R. N.R. N.R. 30.55
extractives ***
N.R. No reported value; * lignin + sugars + proteins. ** Values given as a review of the chemical characterizations
given by other authors. *** Extractives in water and ethanol.

OPW chemical composition differs regarding the constituents and values (see Table 2).
The chemical composition varies depending on factors such as orange variety, size, weather,
soil properties, agrochemicals used, and ripening time. For instance, Citrus × Tangelo
has higher juice yields than the Valencia variety. Thus, Citrus × Tangelo has a lower
peel/pulp ratio. These aspects are related to the morphology of the fruit. On the other
hand, the chemical characterization of OPW chemical composition varies depending on
the agrochemicals used in the agronomic stage. This statement has been corroborated in
other agronomic products such as cocoa, since the use of agrochemicals can increase the
presence of heavy metals such as cadmium and lead. Finally, the lignocellulosic content
can be increased based on the water supply to the orange plant. Indeed, low water levels
produce oranges with a higher peel/pulp ratio [50].
Cellulose, hemicellulose, lignin, ash, protein, fat, sugars, flavonoids, and pectin are the
most common fractions reported in the open literature. The chemical composition analysis
is stated based on the aim of the study [51]. For instance, only pectin is characterized
if the research objective is to valorize this fraction [52]. Proposals for the stand-alone
valorization of OPW can use a partial chemical characterization. Nevertheless, a complete
Biomass 2024, 4 115

chemical characterization is required for proposing OPW valorization processes based on

the biorefinery concept since these facilities allow for the upgrading of almost a fraction
of the raw material into a series of value-added products and energy vectors [53]. A
complete chemical characterization refers to determining the mass fractions of different
components as much as possible (e.g., bioactive compounds, essential oil, fats, pectin,
cellulose, hemicellulose, lignin, proteins, ashes, minerals, fixed carbon, volatile matter, and
moisture content). Chemical characterization allows us to elucidate the potential upgrading
pathways and biorefinery schemes for the integral OPW processing. Indeed, the biorefinery
concept has been applied to upgrade OPW at different levels [54,55].
OPW valorization has been guided toward several important high value-added com-
pounds such as food-grade additives, D-limonene, dietary fibers, flavonoids, anthocyanins,
carotenoids, and citric acid. Several OPW upgrading routes have been proposed based
on the chemical composition. The OPW upgrading pathways are related to physical,
thermochemical, biotechnological, and chemical processes. Physical upgrading has been
applied to obtain essential oil, polyphenolic compounds, and terpenes by steam distil-
lation and solvent extraction, respectively [56,57]. Thermochemical processing has been
reported for producing energy vectors (e.g., biochar, ethanol, pellets, and butanol) and
bioenergy [58–60]. Biotechnological upgrading refers to using microorganisms and en-
zymes to produce value-added products such as organic acids, alcohols, biogas, and ethers.
The most common biotechnological pathways for upgrading OPW are related to the pro-
duction of lactic acid [61], biogas [62], ethanol [14], mucic acid (i.e., galactaric acid) [40],
docosahexaenoic acid [63], and sugars [52]. Finally, chemical routes have been applied to
produce sulfonated carbon catalysts and polyurethane foams [64,65].
OPW valorization can also be classified depending on the technological readiness level
(TRL) of the upgrading process. Indeed, the TRL of the production process is a key factor in
elucidating those products with a high potential to be implemented at the industrial level.
Applications with low TRL (i.e., 1–5) are addressed to obtain high value-added compounds
through biotechnological and chemical pathways [48], for instance, fermentation products
after pectin and cellulose hydrolysis. This statement is true when analyzing the research
data related to the OPW conversion.
In contrast, high TRL (i.e., 6–9) applications are addressed to obtain products derived
from thermochemical and physical processes such as combustion, torrefaction, pelletizing,
and milling [66]. These mature upgrading processes are guided to produce pellets, animal
feed, compost, and bioenergy [66–68]. These products can be produced at different scales,
promoting rural bioeconomy trends or market alternatives at regional and national levels.
In contrast, the scientific perspective requires more effort to scale up novel technologies and
processes. Nevertheless, the high market value and bio-based plus can boost new market
trends to replace oil-based products. Therefore, more efforts are necessary to decrease the
gap between academics and the industry toward boosting a bioeconomy model based on
the valorization of this agro-industrial waste to increase the product portfolio of the orange
industry. Several alternatives for valorizing OPW are presented in Figure 7.
Different biorefinery schemes addressed to upgrade OPW are presented in Figure 8.
OPW-based biorefineries have involved valorization technologies such as anaerobic diges-
tion, simultaneous saccharification and fermentation, pyrolysis, combustion, pyrolysis, and
pelletizing, among others. Several authors have proposed and studied different biorefinery
configurations [67–69]. The integral OPW upgrading is a potential option to produce differ-
ent value-added products. Nevertheless, technical, economic, environmental, and social
assessments are necessary to define feasible biorefinery schemes for industrial analysis.
The link between academics and the industry is the analysis of the abovementioned factors,
since these analyses elucidate potential options and investment requirements.
Biomass 2024, 4 116
Biomass 2024, 4, FOR PEER REVIEW 10

Figure 7. OPW-based products considering different perspectives: (i) academic research and (ii) in-
Figure 7. OPW-based
dustrial upgrading. products considering different perspectives: (i) academic research and
(ii) industrial upgrading.
4. OPW as a Source of Bioactive Compounds
4. OPW OPW as a Source
has beenof Bioactive
considered Compounds
a raw material for producing several products. Neverthe-
OPW
less, has been
bioactive considered
compound a rawhas
extraction material forofproducing
been one several
the most studied products.
areas Nevertheless,
[15,70]. OPW
has been
bioactive recognizedextraction
compound as a potential hassource
been ofoneantioxidants,
of the most phenolic compounds,
studied and
areas [15,70]. OPW
nutraceutical products [57]. Therefore, several extraction methods
has been recognized as a potential source of antioxidants, phenolic compounds, and have been reported.
This review paper focuses on the extraction of bioactive compounds using different tech-
nutraceutical products [57]. Therefore, several extraction methods have been reported. This
nologies such as agitated solvent extraction, microwave-assisted extraction, ultrasound-
review paper
assisted focuses and
extraction, on the extraction
supercritical of bioactive
fluid compounds
extraction [9,71]. usingcompounds
Polyphenolic different technologies
are
suchbioactive
as agitated solvent
substances extraction,
found in different microwave-assisted extraction,
plants, fruits, and vegetables. Theseultrasound-assisted
compounds
extraction,
present and supercritical
antioxidant properties,fluid extraction
sensory [9,71]. Polyphenolic
characteristics, and nutritionalcompounds are bioactive
benefits. For these
reasons, found
substances polyphenolic compounds
in different are widely
plants, produced
fruits, at the industrial
and vegetables. level.
These These com- present
compounds
pounds can
antioxidant be applied
properties, in different
sensory sectors. For instance,
characteristics, polyphenolic
and nutritional compounds
benefits. are reasons,
For these
used in cosmetics and paints, as coloring and flavoring in the food industry, as ingredients
polyphenolic compounds are widely produced at the industrial level. These compounds
in nutraceuticals, as dietary supplements, as additives to antibiotics, and in anti-inflam-
can be applied in different sectors. For instance, polyphenolic compounds are used in
matory and antiallergic medicines in the pharmaceutical industry. The polyphenolic com-
cosmetics
pound andmarketpaints, as coloring
will increase andfew
in the next flavoring in the
years, which willfood industry,
increase as ingredients
the interest of dif- in
nutraceuticals, as dietary
ferent industries to producesupplements,
them [72]. as additives to antibiotics, and in anti-inflammatory
and antiallergic
OPW is amedicines in the pharmaceutical
source of polyphenolic compounds. Gallicindustry. The acid,
acid, ferulic polyphenolic
and para-cou- compound
maric
market acidincrease
will are the most
in important
the next compounds
few years,present.
whichThese
will compounds
increase the caninterest
be extracted
of different
throughtodifferent
industries produce ways.
themSupercritical
[72]. fluid extraction, conventional solvent extraction, mi-
crowave-assisted extraction, and the utilization of deep eutectic solvents are some of the
OPW is a source of polyphenolic compounds. Gallic acid, ferulic acid, and para-
ways reported in the open literature [73]. The methods, conditions, and typical yields are
coumaric acid are
summarized the 3.most important compounds present. These compounds can be
in Table
extracted through different ways. Supercritical fluid extraction, conventional solvent
extraction, microwave-assisted extraction, and the utilization of deep eutectic solvents are
some of the ways reported in the open literature [73]. The methods, conditions, and typical
yields are summarized in Table 3.

Table 3. Total polyphenolic compound (TPC) yields using different methods.

Extraction Method Conditions Yield * Ref.

Agitated solvent Ethanol: 80%; temperature: 35 ◦C 15.80 mgGAE/g RM [57]
Microwave-assisted Power: 125 W; temperature: 35 ◦C 23.40 mgGAE/g RM [57]
Supercritical fluid Temperature: 40–60 ◦ C; pressure: 15–35 MPa 18–21 mgGAE/g RM [78]
Choline chloride + glycerol or ethylene glycol, time:
Deep eutectic solvents 1.28–2.91 mgGAE/g RM [57]
100 min, and temperature: 30 ◦ C
Ultrasound-assisted + Pulse Electric field Ethanol: 50%, time: 30 min, and temperature: 35 ◦ C 34.71 mgGAE/g RM [16]
* RM: raw material dry weight.
Biomass 2024, 4, FOR PEER REVIEW 11
Biomass 2024, 4 117

17.3 g/kg OPW 0.59 g eq GA/kg OPW 0.24 kg/kg OPW

1.57 g/kg OPW 17.4 g/kg OPW

Essential oil extraction Pectin extraction

Essential oil extraction Pectin extraction Polyphenols extraction
Microwave Microwave
Microwave-assisted Conventional Ultrasound-assisted
Hydrodiffusion and Hydrodiffusion and
hydrodistillation hydrodistillation extraction
Gravity Gravity

16.57 g/kg OPW 0.825x10-2 g hesperidin/g OPW 0.43 g/g OPW 23.25g/g OPW 0.77 g/g OPW

Essential oil extraction Polyphenols extraction Succinic acid

Controlled pressure drop Ultrasound-assisted Essential oil extraction Pectin extraction
production
technology extraction Water extraction Dilute acid hydrolysis
Fermentation

0.4 g/g OPW 65 g/g OPW 0.61 g/g OPW 10.35 g/g OPW 89.38 Nm3/Ton OPW

Dietary fiber
Essential oil extraction Essential oil extraction Pectin extraction Biogas production
Wet milling, Dryer,
Steam distillation Steam distillation Dilute acid hydrolysis Anaerobic digestion
Seiving

60 g/g OPW 27 g/g OPW 0.5 g/g OPW 13.24 g/g OPW 43 g/L 0.6 m3/kVolatil Solid OPW

Bio-oil Charcoal
Essential oil extraction Pectin extraction Ethanol production Biogas production
Milling, drying, Milling, drying,
Solvent extraction Dilute acid hydrolysis Fermentation Anaerobic digestion
pyrolysis pyrolysis

Experimentalbiorefineries
Figure8.8.Experimental
Figure biorefineriesfor
forOPW
OPWvalorization.
valorization.The
Thebiorefineries
biorefinerieshave
havebee
beeproposed
proposedby
byseveral
severalauthors
authors[41,55,67,68,74–77].
[41,55,67,68,74–77].
Biomass 2024, 4 118

Solvents used for polyphenolic compound extraction are a key point for defining the
final extract application. Indeed, solvents such as ethanol, acetic acid, water, or mixtures of
both have been reported in the open literature as promising solvents, since these have been
generally recognized as safe (GRAS) for use in the cosmetic and food industries [79]. New
methods for extracting bioactive compounds have been reported in the open literature
(e.g., deep eutectic solvents and pulse electric field). These novel extraction methodologies
are addressed to improve extraction under lower conditions of temperature and solvent
concentration. Nevertheless, these research efforts must be contextualized in a real process
since the technological readiness level (TRL) of the new extraction methods is lower
than seven (i.e., system prototype demonstration in a space environment). In addition,
the economic and environmental performance of these extraction methods has not been
reported widely in the open literature. Thus, this research area has been identified as a
promising field for new developments.
OPW is considered an essential oil source. Essential oil is a terpenes combination
produced by plants as secondary metabolites. Thus, these components are not needed
for plant growth. The most important terpene produced in oranges is D-limonene. This
compound can be found in higher quantities (i.e., concentrations higher than 90% %wt.) in
OPW essential oil. Nevertheless, compounds such as camphene, α-pinene, and β-pinene
can be extracted. Several methods for extracting essential oil have been researched. These
methods are related to the dilation of the cell wall and the disruption of the OPW ligno-
cellulosic matrix. The essential oil extraction methods are cold press, solvent extraction,
steam distillation, supercritical fluids, and microwave-assisted extraction. The methods,
conditions, and typical yields of essential oil extraction are summarized in Table 4.

Table 4. Common OPW essential oil extraction yields after using different methods.

Extraction Method Conditions Yield Ref.

Solvent: hexane, temperature: 80 ◦ C–100 ◦ C, and time:
Soxhlet extraction 0.57–3.24% [80]
120–240 min.
Temperature: 40 ◦ C, pressure: 20 MPa, and
Supercritical fluid extraction 4–12% [9]
CO2 ratio: 5–75 kg/kg peel
Steam explosion Pressure: 10 bar; time: 240 s 1.34% [81]
Hydrodistillation N.R. 1.2% [82]
Steam distillation Time: 45 min 1.09% [82]
Microwave-assisted steam distillation Time: 35 min; power: 150 W. 1.150% [82]

Finally, OPW can supply healthy properties to dietary supplements through phyto-
chemicals such as vitamin C, folic acid, potassium, pectin, polyphenols, minerals, dietary
fibers, essential oils, and carotenoids which present better antioxidant, disease-preventive
properties than other parts of the fruit. In this sense, several health uses of orange peel
can be cited: citrus flavonoids can replicate hepatic lipid metabolism, cure scurvy, and
degenerative diseases [83,84]. The food and functional products industry has shifted its
efforts to bio-based ingredients that can contribute to human health more than synthetic
ingredients to establish a circular bioeconomy. OPW versatility encourages us to research
the production of food products. Table 5 presents some studies conducted for OPW to
obtain food products.
Biomass 2024, 4 119

Table 5. Food products based on bioactive compound extraction from OPW.

Product Features and Uses Technology and Complexity Product Yield

These compounds present antioxidant
properties, sensory characteristics, and
nutritional benefits. In fact, these
OPW is a source of polyphenolic Solvent extraction [80]:
compounds can be applied in different
compounds [68]. Indeed, Ethanol 80% v/v, 35 ◦ C,
sectors. For instance, polyphenolic
hesperidin, narangin, gallic acid, 60 min, and 15.80 mgGAE/g.
compounds are used in cosmetics and
ferulic acid, and para-coumaric acid Microwave-assisted
paints, as coloring and flavoring in the
are the most important compounds extraction [80]:
food industry, as ingredients in
present in OPW [69]. These ones 125 W, 35 ◦ C, and
nutraceuticals, as dietary supplements,
can be extracted through different 23.40 mgGAE/g.
Polyphenolic as additives to antibiotics, and in
methods. Supercritical fluid Supercritical fluid
compounds anti-inflammatory and antiallergic
extraction, conventional solvent extraction [78]:
medicines in the pharmaceutical
extraction, microwave-assisted 40–60 ◦ C, 15–35 MPa, and
industry [8]. The polyphenolic
extraction, and the utilization of 18–21 mgGAE/g.
compound market will increase in the
deep eutectic solvents are some of Deep eutectics solvents [57]:
next few years, which will increase the
the ways reported in the open Choline chloride + glycerol or
interest of different industries to
literature to obtain polyphenolic ethylene glycol, 100 min, 30 ◦ C,
produce them. Modern studies show
compounds from orange peel [12]. and 1.28–2.91 mgGAE/g.
the use of OPW in various
pharmaceutical/nutraceutical
products [67].
These methods are related to the
dilation of the cell wall as well as
Steam distillation [82]:
the disruption of the lignocellulosic
45 min and 1.095% w/w.
matrix of the OPW. The physical
Essential oil is a combination of Hydrodistillation [81]:
methods used to remove essential
terpenes produced by plants as 45 min and 1.2% w/w.
oil are distillation (steam,
secondary metabolites. Thus, these Steam explosion [81]:
steam/water. and water) and cold
components are not essential for plant 10 bar, 240 seg, and
pressing, since cold pressing is the
growth. The most important terpene 1.34% w/w.
conventional method for the.
produced in the orange fruit is Supercritical fluid
Essential oil However, essential oils have some
limonene. This compound can be extraction [9]:
disadvantages (the elevated
found in higher quantities (i.e., 40 ◦ C, 20 MPa, CO2 ratio
temperatures and large time of the
concentrations higher than 90%) in the 5–75 kg/kg peel, and
extraction). These shortcomings
orange peel essential oil. Nevertheless, 1.34% w/w.
have boosted the use of new
other compounds such as camphene, Microwave-assisted steam
technologies such as supercritical
α-pinene, and β-pinene can be found. distillation [82]
fluid extraction, ultrasound
35 min, 150 W, and
extraction, subcritical water
1.150% w/w.
extraction, and
microwave-assisted extraction.

5. Case Study: Bioactive Compound Extraction from OPW Using Different Methods
5.1. Raw Material Source and Conditioning
OPW from an orange juice factory (FLP Procesados) located in Colombia was used
as the raw material for assessing the extraction performance of different methods. The
orange juice company has a constant supply of 200 tons/month. The orange fruits are
harvested from nearby fields (4◦ 59′ 43.4′′ N 75◦ 36′ 07.2′′ W). OPW is obtained by the indus-
trial mechanical extraction of the fruit juice. The OPW samples were frozen at −4 ◦ C for
preservation after the extraction process. Then, the samples were dried in a convective
oven at 40 ◦ C until reaching a moisture content lower than 15%.
OPW samples were milled to a particle size of 0.4 mm (i.e., ASTM 40 Mesh). This
was carried out in a knives mill (Gyratory mill SR200 Gusseisen, Retsch GmbH, Haan,
Germany). The decrease in particle size guarantees the homogeneity of the sample and
increases the transfer area in the extraction of polyphenolic compounds.
Biomass 2024, 4 120

5.2. Extraction Methods

OPW has been used as a raw material for extracting bioactive compounds using
several technologies such as agitated solvent extraction, ultrasound-assisted extraction,
and Soxhlet extraction. All of the assays were conducted using 4 g of OPW. The solid to
liquid ratio was 1:100.

5.2.1. Agitated Solvent Extraction (SLE)

Agitated solvent extraction was conducted using the conditions shown in Table 6 [41].
The OPW samples were mixed in an Erlenmeyer with the solvent. The extraction was
carried out at room temperature (25 ◦ C) in a shaker (Pro Digital Orbital Shaker SK-O330)
at 200 rpm. The solvent was a mixture composed of 70% methanol, 28% water, and 2%
acetic acid [10]. This mixture was selected since high hesperidin (an important flavone)
extraction yields can be obtained [10]. After the extraction time (40 min), the mixture was
vacuum filtered. The extract was stored in an amber bottle at 4 ◦ C to avoid polyphenolic
compound degradation. The solid was dried in a convective oven at 40 ◦ C until it reached
a constant weight.

Table 6. Extraction methods and conditions applied to OPW [41,51,85].

Method Temperature (◦ C) S:L Time (min) Conditions

SLE 25 1:100 40 200 rpm
UAE 25 1:100 40 30 kHz; 100% amplitude
SE Boiling temperature 1:100 40 N.A.*
SLE + UAE 25 1:100 40 200 rpm
SFE 70 N.A. 60 350 bar
* N.A. Not Apply.

5.2.2. Ultrasound-Assisted Extraction (UAE)

The ultrasound-assisted extraction process (UAE) was carried out using the compact
lab homogenizer UP-50H (Hielscher Ultrasound Technology) in a continuous pulse cycle.
This equipment allows for the sonication of samples using a sonotrode. The amplitude
was set to 100%. This value was kept constant in all assays. The extraction process was
carried out with a probe working at 30 kHz. The provided power was 50 W. The operating
conditions are shown in Table 6. These operating conditions were based on the results
reported by Li et al. [83]. After the extraction time, the mixture was vacuum filtered. The
extract was stored at −4 ◦ C, and the solid was dried at 40 ◦ C in a convective oven until it
reached a constant weight [85].

5.2.3. Soxhlet Extraction (SE)

The sample was placed in a porous vessel (thimble). Then, milled OPW was placed
into a Soxhlet apparatus working at constant reflux for 40 min. The extracts were stored in
amber bottles at a temperature of 4 ◦ C. The solid was dried at 40 ◦ C in a convective oven
until it reached a constant weight [86]. The Soxhlet extraction was conducted following
the procedures described by the National Renewable Energy Laboratories (NREL) for
extracting taxes, soluble sugars, and other polar components [87].

5.2.4. Agitated Solvent and Ultrasound-Assisted Extraction (SLE + UAE)

The extraction consisted of subjecting the mixture to a sound for 10 min (using the
UP50H Ultrasound Processor Hielscher Ultrasound Technology), after which time the
mixture was subjected to agitated solvent extraction for 30 min at room temperature. This
extraction method was based on previous experiences related to the bioactive compound
extraction from fruit wastes [41,51,85]. Then, the mixture was vacuum filtered. The extract
Biomass 2024, 4 121

was stored at −4 ◦ C, and the solid was dried at 40 ◦ C in a convective oven until it reached
a constant weight [85].

5.2.5. Supercritical Fluid Extraction (SFE)

The supercritical fluid extraction of bioactive compounds from OPW was conducted
using lab-scale equipment (working volume 254 mL). The extraction conditions are pre-
sented in Table 6. The sample was introduced into the extraction tank. Carbon dioxide
(CO2 ) was used as the solvent. A solid to solvent (CO2 ) ratio of 1:18 and a solid to co-solvent
ratio (ethanol 10% + water 90%) of 1:5 were fixed. The extracts obtained were stored in
amber containers at a temperature of 4 ◦ C. Restrepo-Serna et al. [88] has described the used
equipment in previous studies.

5.3. Quantification of Phenolic Compound Content, Total Antioxidant Capacity, and

Hesperidin Content
The global yield after the extraction process was determined to elucidate the weight
loss after the extractions. The total phenolic compound content (TPC), total antioxidant
activity (TAA), and hesperidin content were determined for the OPW extracts resulting
from the above-described experiments. TPC allows for the determination of any phenolic
compound present in the extracts. TAA allows for the estimation of the antioxidant activity
of the extracts by an inhibition method. Finally, the hesperidin content was determined
via high-performance liquid chromatography (HPLC). These assays provide sufficient
information for analyzing potential valorization pathways based on the extraction of the
bioactive compounds.

5.3.1. Global Yield

The global yield was calculated as the ratio between the sample weights before and
after extraction. This indicator helps to determine the best extraction method through
weight loss. Nevertheless, the global yield does not provide specific information about the
extracted compounds.

ODbefore − ODafter
 
Global Yield (%) = × 100 (1)
ODbefore

where OD before is the oven-dried sample before extraction and OD after is the oven-dried
sample after extraction.

5.3.2. Total Polyphenol Content (TPC)

The total polyphenol content was measured with the Folin–Ciocalteu colorimetric
method with modifications [85,89]. The method consists of mixing 150 µL of the extract
with 2.4 mL of distilled water, 150 µL of Folin–Ciocalteu solution (1N), and 300 µL of
sodium carbonate (20% w/v). The mixture was incubated for 2 h in the absence of light. Ab-
sorbance was read at 765 nm in a spectrophotometer of microplates (SpectraMax ABS Plus,
Molecular Devices, LLC, San Jose, CA, USA) linked to the software SoftMax Pro v.7.0 [85].
A calibration curve was prepared at different dilutions of gallic acid from the stock solution.
Distilled water was used as blank. The total polyphenol content is expressed in mg of gallic
acid equivalent per 100 g of dry sample (mg GAE/100 g sample).

5.3.3. Total Antioxidant Activity (TAA)

The antioxidant activity was measured by the inhibition of the DPPH (2, 2-diphenyl-1-
picryl-hydrazyl-hydrate) radical and the ABTS+ (2, 2′ -azino-bis-(3-ethylbenzothiazoline-6-
sulphonic acid) cation radical decolorization test. The DPPH radical inhibition assay was
conducted according to the method described by Marinova et al. [90], Molyneux et al. [91],
and Brand-Williams et al. [92]. The reaction was performed in a spectrophotometer of
microplates (SpectraMax ABS Plus) by mixing 10 uL of OPW extract with 200 uL of DPPH
solution at 60 uM. The mixtures were allowed to react for 1 h in the absence of light. The
Biomass 2024, 4 122

samples were measured in a spectrophotometer of microplates (SpectraMax ABS Plus,

Molecular Devices, LLC, San Jose, CA, USA) linked to the software SoftMax Pro v.7.0
at a wavelength of 517 nm [85]. The stock solution was prepared using ethanol. The
radical inhibition was calculated using Equation (2). This equation has been reported
everywhere [79]. A calibration curve was prepared with a standard solution of Trolox
diluted in ethanol (100, 200, 250, 300, 350, 400, and 430 µM). Inhibition was reported
considering the following units: µmol of Trolox/100 g of dry sample.
 
Af
Inhibition of absorbance λ517 = 1 − × 100 (2)
Ao

The ABTS+ cation radical decolorization assay was determined based on the method
described by Re et al. [93] and Ozgen et al. [94]. Dilutions of 1:150, 1:300, and 1:500 of
the samples were prepared in ethanol. A total of 150 mL of extract was mixed with 3 mL
of 60 µM solution of ABTS. This mixture was stirred and left in an ultrasound bath at
room temperature for 20 min. Then, the samples were stored in the dark at 4 ◦ C for 24 h.
After this time, the solution was diluted with 20 mM of acetate buffer solution (pH 4.5)
to an absorbance of 0.700 ± 0.01 at 734 nm. The mixture was left for 1 h in the absence
of light. The samples were measured in a spectrophotometer of microplates (SpectraMax
ABS Plus) linked to the software SoftMax Pro v.7.0 at a wavelength of 734 nm [85]. The
inhibition percentage was calculated using Equation (2). The results were reported as µmol
of Trolox/100 g of dry sample.

5.3.4. Hesperidin Quantification

Hesperidin quantification was performed via high-performance liquid chromatog-
raphy (HPLC) with a UV-visible detector (LC-2010A HT—Shimadzu, Bogotá, Colombia).
The chromatographic method reported by Adam [95] was used. The chromatographic
separation was performed with a C18 column (150 mm, 4.6 mm, and 5 µm). An isocratic
mobile phase condition was used. The mobile phase was composed of two solvents, 50%
methanol (solvent A) and 50% water–phosphoric acid at a ratio of 99.9: 0.1 (solvent B).
The flow rate, injection volume, column temperature, and absorbance were 0.9 mL/min,
20 µL, 30 ◦ C, and 280 nm. Hesperidin quantification was carried out using the standard
internal method.

5.4. OPW Extracts: Results and Discussion of the Case Study

The case study was proposed to evaluate the best polyphenolic compound extraction
method using an acidified methanol solution and ethanol. The acidification of the solution
was carried out to dilate the cell membrane of raw materials [73]. Different authors report
higher extraction yields of polyphenolic compounds with acidified solvents. For example,
Bisognin et al. [96] reported an increase of about 13% in the TPC for Ilex paraguariensis leaf
with a solution of methanol (70% v/v) and hydrochloric acid (1% v/v). Piovesana et al. [97]
presented the use of acidified water as a better extraction solvent to obtain total phenolic
acids, anthocyanins, flavonoids, and phenolic compounds compared to other studies using
extraction with industrial organic solvents for Hibiscus sabdariffa L. Solvent acidification
disrupts the lignocellulosic matrix of biomass. Thus, higher extraction yields can be
achieved. Some phenolic compounds, flavonoids, and anthocyanins are covalently bound
to the cell membrane layers of the raw material. The solvent acidification makes these layers
more permeable (i.e., cellulose, hemicellulose, lignin, and pectin). Thus, the solvent can
extract phenolic compounds more easily than without an acidified solvent. The addition
of weak acids, such as citric acid, is recommended at pH between 3 and 4.8 to increase
flavonoid extraction [98]. For this reason, this work studied the mixture of methanol,
water, and acetic acid as a solvent in four (agitated solvent extraction, ultrasound-assisted
extraction, Soxhlet extraction, and agitated solvent and ultrasound-assisted extraction)
extraction methods. In the case of supercritical fluid extraction, the solvent used in the test
 to increase flavonoid extraction [98]. For this reason, this work studied the mixture
methanol, water, and acetic acid as a solvent in four (agitated solvent extraction, ultr
sound-assisted extraction, Soxhlet extraction, and agitated solvent and ultrasound-a
Biomass 2024, 4 sisted extraction) extraction methods. In the case of supercritical fluid extraction, 123 the so
vent used in the test was carbon dioxide. To solubilize hesperidin, a mixture of ethano
water was analyzed as a co-solvent. The overall extraction performance results are pr
was carbon dioxide. To solubilize hesperidin, a mixture of ethanol–water was analyzed as
senteda in Figure 9.
co-solvent. The overall extraction performance results are presented in Figure 9.

80
60.35
70
51.75
46.14 47.51
Global yield (w/w %)

60

50

40

30
17.75
20

10

0
Agitated solvent Ultrasound-assited Agitated solvent Soxhlet extraction Supercritical fluid
extraction extraction and Ultrasound- extraction
assited extraction

Figure 9. Global yield of different extraction methods applied to OPW.

Figure 9. Global yield

Soxhlet of different
extraction extraction
(SE) had methods
the highest globalapplied to OPW.
performance with a value of 60.35%.
Ultrasound-assisted extraction (UAE) was the method with the second highest extraction
Soxhlet extraction
performance. On the(SE) other had
hand, theSLEhighest
+ UAEglobal performance
had a yield of 47.51%.with a value
Finally, of 60.35%
agitated
solvent extractionextraction
Ultrasound-assisted (SLE) and supercritical
(UAE) was fluid
theextraction
method(SFE) withhad thea second
yield of 46.14%
highest andextractio
17.75%, respectively. The global yield refers to the loss of mass suffered by the sample in
performance. On the other hand, SLE + UAE had a yield of 47.51%. Finally, agitated so
the extraction time. Thus, higher yields are related to higher extraction performance. The
vent extraction (SLE)
SE global yield and supercritical
increased by 23.54% compared fluid extraction (SFE) The
to the SLE process. hadUAEa yield
globalofyield
46.14% an
17.75%,
wasrespectively.
lower (14.25%) Thethan global
the SLE. yield
On refers
the otherto hand,
the lossthe of
SLEmass+ UAEsuffered
process by the sample
obtained
a lower performance than the UAE process (8.2%). SFE had an
the extraction time. Thus, higher yields are related to higher extraction performance. Thextraction performance
3.4-fold
SE global yieldhigher than theby
increased SE23.54%
method.compared
The low overall
to theperformance
SLE process. in terms
The UAE of lossglobal
of yiel
mass in the extraction with supercritical fluids is because by varying the conditions of
was lower (14.25%) than the SLE. On the other hand, the SLE + UAE
temperature, pressure, and concentration of the co-solvent, the extraction becomes selective
process obtained
lower to
performance
a metabolite ofthan the[99].
interest UAE process (8.2%). SFE had an extraction performance 3.
fold higher SEthan thebest
was the SE method
method. forThe low overall
extracting compounds performance
(see Figure in9). terms of lossthe
Nevertheless, of mass
process temperature does not guarantee
the extraction with supercritical fluids is because by high-quality extracts, since several polyphenolic
varying the conditions of temper
compounds can degrade at higher temperatures (>50 ◦ C) [100]. For this reason, a compar-
ture, pressure, and concentration of the co-solvent, the extraction becomes selective to
ison not only in terms of global yield must be performed. A comparison between TPC,
metabolite of interest
TAA (ABTS [99]. and value-added compound concentration (e.g., hesperidin) must
and DPPH),
SE
be was the best method for extracting compounds (see Figure 9). Nevertheless, th
performed.
The results obtained
process temperature does notareguarantee
better thanhigh-quality
some studies extracts,
reported in the literature.
since For
several polyphenol
example, Zia-ur-Rehman et al. [101] reported a global extraction
compounds can degrade at higher temperatures (>50 °C) [100]. For this reason, a compa yield of 11% for an ethanol
extractor of dried and ground citrus peel. This result is lower than those presented. The
ison not
sameonly in terms
author reports of global
a yield yield must
of 19.87% be performed.
using methanol A comparison
as a solvent. Goulas et al.between
[102] TPC
TAA (ABTS
reported and DPPH),
a global extractionand yieldvalue-added
with methanolcompound
(100%) of 70.2% concentration (e.g., hesperidin
by Soxhlet extraction for
must be performed.
30 min and a solid/liquid ratio of 1:0.26 w/v. This result is 14% higher than that obtained
The resultsextraction.
after OPW obtainedThis aredifference
better than couldsome
be attributed
studiesto reported
the solid/liquid
in the ratio applied For e
literature.
in this case study. Goulas et al. [102] obtained more concentrated extracts, so the weight
ample, Zia-ur-Rehman et al. [101] reported a global extraction yield of 11% for an ethan
loss was higher. However, this result does not reflect higher concentrations of polyphenolic
extractor of dried(e.g.,
compounds andhesperidin).
ground citrus peel. This
The extraction result is lower
of flavonoids, thanlimonoids,
glucosides, those presented.
and Th
same organic
authoracidsreports a yieldacid
(e.g., ascorbic of 19.87%
and citric using
acid) canmethanol as amethanol
be higher using solvent.asGoulas
the solvent.et al. [10
The TPC results are presented in Figure 10.
reported a global extraction yield with methanol (100%) of 70.2% by Soxhlet extraction fo
30 min and a solid/liquid ratio of 1:0.26 w/v. This result is 14% higher than that obtaine
after OPW extraction. This difference could be attributed to the solid/liquid ratio applie
in this case study. Goulas et al. [102] obtained more concentrated extracts, so the weigh
loss was higher. However, this result does not reflect higher concentrations
 polyphenolic compounds (e.g., hesperidin). The extraction of flavonoids, glucosides, li-
Biomass 2024, 4
monoids, and organic acids (e.g., ascorbic acid and citric acid) can be higher using meth-
124
anol as the solvent. The TPC results are presented in Figure 10.

800

700
TPC (mgGAE/g OPW, db)

600

500

400

300

200

100

0
Agitated solvent Ultrasound-assisted Agitated solvent Soxhlet extraction Supercritical fluid
extraction extraction and Ultrasound- extraction
assisted extraction

Figure 10. TPC content after OPW extraction by applying different methods.
Figure 10. TPC content after OPW extraction by applying different methods.
The TPC content in the extracts allows us to elucidate the extraction efficiency better
thanThe
theTPCglobalcontent
yield. Inin the
the global
extracts allows
yield, us to
the loss ofelucidate
mass sufferedthe extraction
by the samplesefficiency
is not better
directly related to the extraction of polyphenolic compounds. Conversely,
than the global yield. In the global yield, the loss of mass suffered by the samples is not other bioactive
compounds
directly relatedpresent
to the in extraction
OPW can beofsolubilized
polyphenolic(e.g., soluble
compounds.sugars).Conversely,
Indeed, OPW extracts
other bioactive
can have a soluble sugar concentration between 29 and 44 g/100 g of sample [90]. The
compounds present in OPW can be solubilized (e.g., soluble sugars). Indeed, OPW ex-
TPC content has a similar behavior to global yield. However, when comparing UAE with
tracts can have a soluble sugar concentration between 29 and 44 g/100 g of sample [90].
SE, the TPC content was 38.84% higher. In the SLE + UAE case, the TPC content was
The TPCto
similar content
SE (2.53% haslower).
a similar behavior
Finally, the SFEto global
provides yield.
a TPC However, whenhigher
content 3-fold comparingthan UAE
with
SE. SE,
Thisthe TPCreflects
result content thewashigh38.84% higher.
potential of SFEIntothe SLE extracts
obtain + UAE case, thepolyphenolic
rich in TPC content was
similar to SE (2.53%
compounds. Saini etlower).
al. [91]Finally,
reportedthe SFE content
a TPC provides of a28.30
TPCmg content
GAE/g 3-fold higher
of citric than SE.
waste
This resultultrasound-assisted
through reflects the high potential
extraction ofwithSFE to obtain
acetone and extracts
water as rich in polyphenolic
the solvents (1:3 v/v). com-
The yield
pounds. obtained
Saini in this
et al. [91] case study
reported by UAE
a TPC wasof
content 8.18-fold
28.30 mg higher
GAE/g thanofthat reported
citric wasteby through
Saini et al. [91]. Moreover, the SLE + UAE process obtained a yield 8.59-fold
ultrasound-assisted extraction with acetone and water as the solvents (1:3 v/v). The yield higher than that
reported by Saini et al. [91]. Goulas et al. [102] reported a TPC content of 108.5 mgGAE/g
obtained in this case study by UAE was 8.18-fold higher than that reported by Saini et al.
OPW through Soxhlet extraction. The TPC content was 2.3- and 7.0-fold higher than that
[91]. Moreover, the SLE + UAE process obtained a yield 8.59-fold higher than that reported
reported by Goulas et al. [102]. Therefore, solvent acidification improves polyphenolic
bycompound
Saini et al. [91]. Goulas
extraction. However,et al.
TPC[102] reported
analysis does nota TPC
allowcontent of 108.5if mgGAE/g
us to determine SE is better OPW
through Soxhlet
for hesperidin extraction. The TPC content was 2.3- and 7.0-fold higher than that re-
extraction.
portedTAAby Goulas et al. [102].
was quantified Therefore,
in terms of DPPHsolvent acidification
and ABTS. The resultsimproves
of the OPW polyphenolic
extractions com-
pound extraction.
are presented However,
in Figure TPC analysis
11. Initially, does not
the free radical allow usactivity
scavenging to determine if SE is better
of the extracts
analyzed
for hesperidinby theextraction.
DPPH scavenging assay. The SFE extracts had a higher antioxidant capacity
compared
TAA was to the other extracts.
quantified in terms This
of behavior
DPPH and allows
ABTS. us The
to confirm
resultsthat theOPW
of the hesperidin
extractions
are presented in Figure 11. Initially, the free radical scavenging activity of methods.
content in the supercritical fluid extraction was higher compared to the evaluated the extracts is
Similar results were obtained using the ABTS method.
analyzed by the DPPH scavenging assay. The SFE extracts had a higher antioxidant ca-
SFE had the highest hesperidin extraction yield (see Figure 12). The hesperidin
pacity compared
concentration to the by
increased other
58%,extracts.
compared This behavior
to SLE. allows
In addition, theus to confirm
hesperidin that the hesper-
concentration
idin content in the supercritical fluid extraction was higher compared
was similar in the SLE and UAE processes (increases of 6.16%). Goulas et al. [102] reported to the evaluated
methods.
a hesperidinSimilar
contentresults
of OPWwere of obtained
6.02 g/kg by using thethis
SE. In ABTScase method.
study, a hesperidin content of
8.18SFE
g/kg had the highest
of OPW hesperidin
was obtained extraction
via SFE. This yieldyield (see Figure
is higher 12). reported
than those The hesperidin
in the con-
open literature [102].
centration increased by 58%, compared to SLE. In addition, the hesperidin concentration
was similar in the SLE and UAE processes (increases of 6.16%). Goulas et al. [102] reported
a hesperidin content of OPW of 6.02 g/kg by SE. In this case study, a hesperidin content
of 8.18 g/kg of OPW was obtained via SFE. This yield is higher than those reported in the
open literature [102].
Biomass
Biomass2024,
2024,4,4,FOR
FORPEER
PEERREVIEW
REVIEW 19
19
Biomass 2024, 4 125

250
250
db)
OPW,db)

200
200
Trolox/gOPW,
(umolTrolox/g

150
150

100
100
DPPH(umol

50
DPPH

50

00
Agitated
Agitatedsolvent
solvent Ultrasound-assisted
Ultrasound-assisted Agitated
Agitatedsolvent
solventans
ans Soxhlet
Soxhletextraction
extraction Supercritical
Supercriticalfluid
fluid
extraction
extraction extraction
extraction Ultrasound-assisted
Ultrasound-assisted extraction
extraction
extraction
extraction

(a)
(a)DPPH
DPPHresults
resultsof
ofthe
theorange
orangepeel
peelwaste
wasteextracts.
extracts.
25
25
db)
OPW,db)

20
20
Trolox/gOPW,

15
(umolTrolox/g

15

10
10
ABTS(umol
ABTS

55

00
Agitated
Agitatedsolvent
solvent Ultrasound-assisted
Ultrasound-assisted Agitated
Agitatedsolvent
solventans
ans Soxhlet
Soxhletextraction
extraction Supercritical
Supercriticalfluid
fluid
extraction
extraction extraction
extraction Ultrasound-assisted
Ultrasound-assisted extraction
extraction
extraction
extraction

(b)
(b)ABTS
ABTSresults
resultsof
ofthe
theorange
orangepeel
peelwaste
wasteextracts.
extracts.
Figure
Figure11. Antioxidant capacity
capacityof
of(a) DPPH and (b) ABTS after OPW bioactive compound extrac-
Figure11.
11.Antioxidant
Antioxidant capacity of (a)DPPH
(a) DPPHand
and(b)
(b)ABTS
ABTSafter
after OPW
OPW bioactive
bioactive compound
compound extrac-
extraction.
tion.
tion.

99
88
db)
OPW,db)

77
(g/kgOPW,

66
55
Hesperidin(g/kg

44
Hesperidin

33
22
11
00
Agitated
Agitatedsolvent
solvent Ultrasound-assisted
Ultrasound-assisted Agitated
Agitatedsolvent
solventans
ans Soxhlet
Soxhletextraction
extraction Supercritical
Supercriticalfluid
fluid
extraction
extraction extraction
extraction Ultrasound-assisted
Ultrasound-assisted extraction
extraction
extraction
extraction

Hesperidin contentininthe
Figure 12.Hesperidin
Figure the OPWextracts.
extracts.
Figure12.
12. Hesperidincontent
content in theOPW
OPW extracts.
Biomass 2024, 4 126

6. Conclusions
Factors such as variety, agricultural practices, soil properties, and orange juice pro-
duction methods influence OPW chemical composition. Specific applications based on
OPW chemical composition and production context must be proposed. Thus, several OPW
upgrading possibilities can be implemented at the industrial level. Nevertheless, more
efforts should be made to bring academic proposals to the industrial sector, boosting the
production of high value-added products such as essential oils, antioxidants, and organic
acids. The gap between academics and the industry related to OPW valorization is at-
tributed to the lack of a comprehensive analysis of OPW valorization pathways involving
technical, economic, environmental, and social aspects based on a specific context (i.e.,
research based on industrial and market needs). Thus, more research efforts should be
made on this topic.
OPW chemical composition is the basis for proposing different applications. Never-
theless, stand-alone applications must be evolved into a biorefinery system. This transition
will increase the feasibility of OPW valorization schemes. Bioactive compound extraction
is presented as a fundamental step when valorizing OPW, since these components have
several applications at the industrial level. Exhausted OPW can be used as a source of bulk
chemicals and bioenergy. The technological readiness level (TRL) must be considered when
proposing valorization alternatives since higher innovative processes with a high TRL will
be implemented faster than applications with a low development grade.
Supercritical fluid extraction is one of the most favorable methods to obtain bioactive
or polyphenolic compounds at the technical level since high extraction yields and selectivity
can be obtained. This statement is evidenced in the experimental results obtained in the case
study. Nevertheless, the scale of the process should be analyzed based on economic aspects.
The extraction of hesperidin with carbon dioxide under supercritical conditions yielded 58%
more product than conventional stirred solvent extraction. Thus, this technology can be
proposed as a potential alternative to valorize OPW. Bioactive compound extraction using
methanol and acetic acid as the solvents was higher than the extraction yields reported
in the open literature using other solvents (e.g., ethanol). Thus, the addition of a weak
acid to the extraction process enhances the process. Ultrasound-assisted extraction was
the second-best alternative to extract bioactive compounds. Nevertheless, more efforts are
needed to scale up this technology.

7. Perspectives and Future Work

OPW is a raw material with high availability and the potential to be upgraded for
different value-added products and energy vectors. Nevertheless, the gap between aca-
demics and the industry must be overcome to implement new valorization alternatives.
Indeed, more studies focused on real OPW use as a raw material to give a solution for
industries should be conducted. More contextualized valorization alternatives should be
proposed based on regional and national market needs and technologies with a high TRL
level. In contrast, research studies should present new upgrading alternatives to industrial
stakeholders based on technical, economic, environmental, and social assessment. This fact
will be the starting point to develop a bioeconomy based on the use of residual biomass.
On the other hand, integral OPW upgrading should be based on chemical com-position
analysis and physicochemical characteristics, since more reliable and feasible products can
be proposed. Indeed, bioactive compounds will play an important role in OPW valorization,
but structural polymers (i.e., pectin, cellulose, hemicellulose, and lignin) must be valorized
toward sustainable production. Then, the chemical composition must be considered a key
point when proposing valorization alternatives.
Finally, the assessment of different extraction methods should be addressed to op-
timize the extraction of bioactive compounds considering the origin and variety of the
raw material.
Biomass 2024, 4 127

Author Contributions: Conceptualization, J.C.S.-T., M.O.-S. and C.A.C.A.; formal analysis, C.A.C.A.;
investigation, J.C.S.-T., M.O.-S. and C.A.C.A.; writing—original draft preparation, J.C.S.-T., M.O.-S. and
C.A.C.A.; writing—review and editing, J.C.S.-T., M.O.-S. and C.A.C.A.; supervision, C.A.C.A.; funding
acquisition, C.A.C.A. All authors have read and agreed to the published version of the manuscript.
Funding: This paper is the result of the research work developed through the research project
“Repotenciación y adquisición de equipos para el laboratorio de Equilibrios Químicos y Cinéticas
Enzimáticas para impulsar la línea de investigación dirigida a la extracción y análisis de compuestos
bioactivos y nitrógeno” code 59387 of Vicerrectoria de Investigación y Docencia de la Facultad de
Ingeniería y Arquitectura in Universidad Nacional de Colombia sede Manizales.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflicts of interest.

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