FOOD A N D BIOPRODUCTS PROCESSING 9 O ( 2 0 1 2 ) 606-614

Contents lists available at SciVerse ScienceDirect

Food and Bioproducts Processing IChemE

journal homepage: www.elsevier.com/locate/fbp
ELSEVIER

Review

Proposals for the residues recovery: Orange waste as raw

material for new products
K. Rezzadori", S. Benedetti", E.R. Amante'''*
^ Department 0/Chemical and Food Engineering, Federal University 0/Santa Catarina, EQA/CTC/UFSC, 88040-900 Florianópolis, SC,
Brazil
'' Department o/Food Science and Technology, Center 0/Agricultural Science, Federal University 0/Santa Catarina, Rod. Admar Gonzaga,
1346, Itacorubi, 88034-00 Florianópolis, SC, Brazil

A B S T R A C T

The production of orange juice on an industrial level leads to a considerable quantity of solid and liquid residue
(around 8-20 million tonsy"^ globally), which is still considered as waste or used as a complement in agriculture.
In general, orange residues have no economic value, even though their composition is rich in soluble sugars, cellu-
lose, hemieellulose, pectin and essential oils that could form the basis of several industrial processes. In this study,
information was collected on the technological potential of the solid and liquid residues generated in the processing
of orange juice. Possible applications include human consumption, fertilizer, animal feed, charcoal, adsorption of
chemical compounds, bio-oil production and extraction of essential oils and pectin. In this preliminary study, alter-
natives are proposed for the minimization and recovery of solid and liquid residues generated in the production
of orange juice with a view to the implantation of industrial plants which can reuse this material, in order to add
value to this solid and liquid waste and provide environmental benefits. The alternatives were proposed based on
information and data available in the literature and the concepts of clean technologies.
© 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Residue; Orange juice; By-products; Bio-oil; Pectin; Added value

Contents

1. Introduction 607
2. Residue characterization: orange waste 607
3. Proposals for the use of orange waste 607
4. Case study 608
5. New products from orange waste: proposals and yields 608
5.1. Production of ingredients for animal feed - System 1 609
5.2. Bio-oil and charcoal production - System 2 609
5.3. Essential oil extraction - System 3 609
5.4. Pectin production - System 4 610
5.5. Solid residue as adsorbent - System 5 610
5.6. Integrated process for production of ethanol, biogas and limonene - System 6 612
5.7. Benefits of the proposed systems 612
6. Final considerations 612
Acknowledgments 612
References 612

* Corresponding author. Tel.: +55 48 3721 5371; fax: +55 48 3721 9687.
E-mail address: eamante@cca.ufsc.br (E.R. Amante).
Received 2 March 2012; Received in revised form 28 May 2012; Accepted 17 June 2012
0960-3085/$ - see front matter © 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.0rg/lO.lOl6/j.fbp.2Oi2.O6.OO2
 FOOD A N D B I O P R O D U C T S P R O C E S S I N G
1. Introduction
Orange is a citrus fruit consumed in high quantities all over
the world in the natural and peeled forms and as a juice. It
is associated with a low cost and contains many nutrients
including vitamin C, A and B, minerals (calcium, phosphorus,
potassium), dietary fiber and many phytochemicals, includ-
ing flavonoids, amino acids, triterpenes, phenolic acids and
carotenoids (Melèndez-Martinez et al., 2008; Roussos, 2011)
Oranges are one of the most important commodities in
terms of global agricultural production, ranked in 20th posi-
tion in 2008 and representing around 10.5% of the world fruit
production (Faostat, 2010; Usda, 2010). Brazil is responsible for
around 53% of the orange juice produced worldwide and for
80% of the international trade in this product (Abecitrus, 2008).
According to Faostat, in 2009 the Brazilian orange production
was almost 18 million tons, representing approximately 49%
of the total fruit production in this country.
Duringorange juice production, only around the half of the
fresh orange weight is transformed into juice (Braddock, 1995),
generating great amounts of residue (peel, pulp, seeds, orange
leaves and whole orange fruits that do not reach the quality
requirements), which accounts for the other 50% of the weight
of the fruit and has a moisture content of approximately 82 g
100 g-i (Abecitrus, 2008; Garcia-Castello et al., 2011). This huge
amount of waste is, in most cases, spread on soil in areas
adjacent to the production locations, for its final use as a raw
material in animal feed, or else it is burned (Martin et al.,
2010). This method of waste handling produces highly pol-
luted wastewater in terms of chemical and biological oxygen
values which can negatively affect the soil and the ground and
superficial waters (Braddock, 1995).
One alternative to improve the management of these
residues is the implementation of new processes for their
recovery, for instance, through the production of organic
fertilizers, pectin, bio-oil, essential oils, and antioxidant com-
pounds, or as a substrate for the production of several
compounds with high added value, such as microbial pro-
teins, organic acids, ethanol, enzymes and biologically active
secondary metabolites and adsorbent materials. These are
excellent alternatives to avoid environmental pollution and
to add value to these substances (Abecitrus, 2008).
Due to the great amount of residues generated at orange
production and processing sites this study aims to offer rec-
ommendations for investors or orange processors by gathering
information regarding the technological potential of these
solid and liquid residues. Also, the levels of economic invest-
ment required and the benefits available to industries able to
process this waste and increase its value are discussed, along
with the environmental issues. The results are presented in
the form of a review, contemplating the waste characteriza-
tion and alternative uses of this material, information which
is then used as a basis for calculating the volumes generated
in an orange juice processing company.
2. Residue characterization: orange waste
The valorization of residues requires knowledge of their chem-
ical composition. Orange waste contains 16.9 g 100 g~^ soluble
sugars, 9.21 g 100 g"^ cellulose, 10.5 g 100g-^ hemicelluloses,
and 42.5 g 100 g"^ pectin, which is its most important compo-
nent. Due to its composition being rich in soluble and insoluble
carbohydrates, this by-product shows great potential for use
9 0 ( 2 0 1 2 ) 606-614 607
Orange
Reception
Selection
Cleaning Rejected orange—»-Composting
50% juice-« Juiee extraetion | — • Orange waste—*• Reuse
I I
Filtration
45.5% 0.5%
I solid vvaslc liquid waslc
Pasteurization
I Blending |
I
J
Freezing packing
i
I Storage/Shipping |
Fig. 1 - Flowchart showing orange juice process.
in products with high added value obtained through chemical
or enzymatic hydrolysis and subsequent biological conversion
(Rivas et al, 2008).
The soluble sugars present in orange peel are glucose, fruc-
tose, and sucrose. The insoluble polysaccharides of the cellular
wall of the orange peel are composed of pectin, cellulose, and
hemicelluloses. Pectin and hemicelluloses are rich in galac-
turonic acid, arabinose, and galactose, and also contain small
amounts of xylose, rhamnose and glucose (Grohmann et al.,
1995).
After the extraction of juice from the oranges, the peel,
seeds, and pulp are usually transformed into pelletized bran
for animal feed. Among the liquid residues spilled into the
environment the residue known as "yellow water" is of major
concern since it has a high content of organic matter, making
it an agent with high pollution potential (Tavares et al., 1998).
Some by-products of the citrus industry have expressive com-
mercial value: the essential oils obtained from orange peel are
notable for their use as ingredients in foods, beverages, cos-
metics and perfumes, aromatic essences; d-limonene is used
in the production of inks and solvents; the bran of citric pulp
is employed in the production of animal feed; and orange pulp
is used by the food and beverage industries (Pereira, 2008). The
industrial processing of orange juice is detailed in Fig. 1.
3. Proposals for the use of orange waste
A vast number of promising proposals for the use of orange
waste have been described in the literature. These include the
use of the waste to produce fertilizer, essential oils, pectin,
ethanol, industrial enzymes, single cell proteins, pollutant
absorbents and paper pulp supplements (Siles et al., 2010).
In the search for alternative solutions to the problems asso-
ciated with the discarding of residues, many industries have
been opting for the use of microorganisms as agents to reduce
the organic matter of such materials and eliminate or reduce
toxic compounds. Anaerobic digestion, in which both pollu-
tion control and energy recovery can be achieved, is another
possible way to treat and add value to the abundant orange
peel waste. This process is defined as the biological conversion
of organic material to a variety of end products including 'bio-
gas' whose main constituents are methane (65-70 g 100 g"^)
and carbon dioxide. Martin et al. (2010) have shown that the
anaerobic digestion of orange peel waste after a d-limonene
608 FOOD A N D BIOPRODUCTS PROCESSING 9 0 ( 2 0 1 2 )
extraction reveals higher methane production, providing an
excellent opportunity to integrate this waste into orange juice
manufacturing using a biorefinery approach,
Agroindustrial residues, such as those generated in citric
juice production plants, have also been used as a substrate for
the production of enzymes, Nighojkar et al, (2006) studied the
use of orange peel as a substrate and indueer in the production
of polygalaeturonase by microorganisms and concluded that
orange peel is a very good indueer. Mamma et al, (2008) con-
cluded that it is possible to produce pectinolytic, cellulolytic
and xylanolytic enzymes from the fungal strains of the genera
Aspergillus, Fusarium, Neurospora and Pénicillium and generate
multienzyme activity using a simple growth medium con-
sisting of a solid by-product of the citrus processing industry
(orange peel).
These residues also have high energy value, and they can
help to reduce the dependency on energy purchased for the
generation of heat, vapor, or electricity. Despite the great
opportunities for the use of such residues, there are few exam-
ples in the literature of the application of residues from the
orange agro-industry for energy generating purposes, either
in the form in which they are produced or after their trans-
formation (Widmer et al,, 2010), Before they are used in the
generation of thermal energy, the solid residues from oranges
can be converted into charcoal and into the by-products of
carbonization, which would widen their range of uses and
at the same time facilitate their transportation, storage, and
handling. According to Tienne et al, (2004), the pyrolysis of
orange peel is possible based on the gravimetric income asso-
ciated with the coal and carbon obtained and eoneluded that
the charcoal produetion and utilization of the by-products
from the pyrolysis of peel and orange pulp allow value to
be added to this agroindustrial residue. In addition, the pulp
fruit can be used for bio-oil production also employing pyrol-
ysis (Özbay et al,, 2008), According to Embrapa (2009), orange
waste is a good biomass for bio-oil production, yielding up
to 60 g 100 g"i by weight compared to the raw material used,
i,e,, a ton of solid residue can yield up to 600kg of bio-oil
(Embrapa, 2009),
The citrus processing waste can be used to produce
ethanol, limonene, and other co-products. Extensive work has
been carried out vnth enzymatic hydrolysis to liquefy this
residue and maximize the monomeric sugar content. These
sugars can be subsequently or simultaneously (Wilkins et al,,
2007a,b) converted into ethanol by fermentation, Widmer et al,
(2010) studied the use of citrus processing waste for ethanol
production by saccharification and fermentation processes
and observed that the ethanol yields based on the sugar
content after enzymatic hydrolysis following 48 h of simul-
taneous saccharification and fermentation ranged from 76%
to 94%,
Another quite profitable alternative for the residues gen-
erated during orange processing is the extraction of essential
oils, that is, volatile oils extracted from the citric fruit peel
(Donsi et al,, 2011), These essential oils have several applica-
tions in the pharmaceutical and food industries, d-Limonene
is an oily fraction and it is considered to be one of the purest
sources of monoeyelie terpene (Corazza et al,, 2001; Viuda-
Martos et al,, 2008), Also, these oils ean contain compounds
with biological activity, such as limonoids and their gluco-
sides, which cause the inhibition of cancerous tumors induced
in rats, mice, and hamsters (Reda et al,, 2005), Various tech-
niques can be used for the extraction of essential oil, such
as supercritical extraction, hydrodistillation, distillation and
606-614
microwave, Farhat et al, (2011) studied a new process for the
extraction of essential oil from orange peel called microwave
steam diffusion and eoneluded that it is an efficient method
for the extraetion of essential oil from orange peel, providing
good yields.
The application of alternative materials in the adsorp-
tion of chemical compounds and toxic metals present in
industrial effluents, particularly in research laboratories, are
scarce; however, some studies have shown that this strat-
egy has potential. As an example, it has been demonstrated
that orange pulp is effective for removing heavy metals from
industrial effluents. According to Ajmal et al, (2001), the use of
orange bagasse as an alternative adsorbent is effective in the
removal of Ni from electroplating effluent, where more than
93% of the metal was adsorbed, Pérez-Marín et al, (2008) eval-
uated the use of orange waste in the biosorption of cadmium,
zinc and lead and obtained good results, Biswas et al, (2008)
studied the removal and recovery of phosphorus from water
by means of adsorption onto an orange waste gel loaded with
zirconium and concluded that it is a promising and potentially
attractive adsorbent for treating wastewater contaminated
with inorganic phosphate and consequently provides a step
towards a sustainable society.
The bran of citric pulp, or orange peel bran, is another
very important by-product. This bran is obtained through the
treatment of solid residues and liquid remaining after juice
extraction. The pelletized bran of citric pulp is used as a com-
plement in animal feed, and is well accepted as an ingredient
in bovine feed (Corazza et al,, 2001), The use of industrial
residues derived from citric fruits in animal diets reflects the
importance offibersin the maintenance of the ruminai motil-
ity and also to motivate rumination. However, thisfiberneeds
to be in the appropriate condition. It has been emphatically
stated that the use of fiber in human nutrition is correlated
with the prevention of diseases (Mendonça et al,, 2006),
4. Case study
The quantitative data on the residues generated by the orange
processing industry were obtained from the literature and
from information supplied by a local orange juice production
plant. The proposals to increase the value of the orange waste
will be presented asflowcharts,mass balances and yields for
each system, based on calculations and production data relat-
ing to a large orange juice plant with a daily proeessing rate of
approximately 16,0001, This production will be considered to
estimate both the amount of solid and liquid waste proeessed
and the derivatives produeed,
5. New products from orange waste:
proposals and yields
The characteristics of solid and liquid orange residues suggest
that these waste materials can be used for the development
of new products. This paper proposes six products which
ean be obtained from the solid fraction and four from the
liquid fraetion of the orange waste. The eompany under
study produees 8000 tday"^ of pasteurized and eoncentrated
juice, using 16,000 tday~^ of oranges, with the generation of
80001 day~^ of orange waste (considering 50% of the raw mate-
rial).
The alternatives are presented as systems for the use of
residues from the orange juice industry.
 FOOD A N D BIOPRODUCTS PROCESSING 9 O ( 2 0 1 2 )
Juiee produetion
T T
S.OOOt Solid residue
T methods chemical and/or
Pressing
enzymatic
Drying
T T
Citric pulp
7.2001
Pelletized
Storage/Shipping
Fig. 2 - Flowchart detailing the process involved in the use
of orange peel for animal feed.
5.1. Production 0/ingredients/or animal feed - System
1 It is a black oil with a characteristic odor and high perfor-
Solid waste generated during orange juice production can be
used to produce ingredients for animal feed (fresh or dried
orange pulp). This system includes the most common proce-
dures applied by orange juice production plants regarding the
destination of the residues. Most plants make use of almost
all the residue generated in the industrial process for the pro-
duction of animal feed (Moreira et al., 2004).
The dried pulp it is obtained after two pressings (which
reduces the moisture content to 65-75 g 100 g"^) and drying
(resulting in up to 90 g 100 g^^ dry matter), before being pel-
letized and marketed (Teixeira, 2001). According to the same
author, to facilitate the separation of the water and lessen
the hydrophilic nature of the pectin, the main carbohydrate
present in the pulp, calcium hydroxide or calcium oxide is
added before the pressings. Due to the high water content in
the fresh pulp it is difficult to dry in common industrial drying
devices, while its high content of organic matter means that
it cannot be disposed of easily (Crupi et al., 2001). However,
there are chemical and/or enzymatic methods available that
facilitate the pressing of this waste and reduce its water con-
tent sufficiently to permit it to be dried in a normal industrial
drier (Tripodo et al., 2004).
As shown in Fig. 2, the solid orange waste obtained could
be used as an ingredient for animal feed due to the high con-
tent of sugars, fiber and other residual substances. According
to data found in the literature, in the production of orange
juice the residues correspond to 50% of the raw material.
Therefore, since the processing plant investigated in this case
processes 16,0001 of oranges day-^, around 80001 of solid
and liquid residues are generated daily. Considering that the
liquid residue ("yellow water") corresponds to 0.5 g 100 g"i
(by weight) of the total residue, 401 of liquid residues and
79601 of solid residues are generated daily at this plant.
Considering that the feed produced from that residue has
10g 100 g-i moisture, from 80001 of solid residues 72001 of
bran can be obtained daily and used as an ingredient for
animal feed.
5.2. Bio-oil and charcoal production - System 2
Currently, the pyrolysis of biomass is of particular interest
as a means to produce bio-oil, which is a valuable product.
606-614 609
Juiee produetion
8.0001- Solid residue
Hoi gas
T power generation
Milling
Gas-liquid separation
Drying
•miergasJ Downflow reactor
700 °C
700 "C I -L
Bio-oil 4.8001
864 t Charcoal
Fig. 3 - Flowchart showing process involved in bio-oil and
charcoal production.
Although research in this area is still in the initial stages, bio-
oil has great potential to replace petroleum, with advantages
in various applications. The bio-oil is a renewable organic fuel
derived from the processing of agricultural and forest residues.
mance and can be obtained not only from pyrolysis but also
thermal degradation (Embrapa, 2009). Bio-oils may be used
for many applications for example as a transport fuel or as
an additive to conventional fuels and to feedstock chemicals.
According to Haykiri-Acma et al. (2010) and Rutkowski (2011),
the biomass used as an energy source is mainly a mixture
of three main components, i.e., cellulose, hemicellulose and
lignin. Due to the high content of these components in the
orange waste, the residue generated from orange juice pro-
duction is considered a good biomass for the production of
bio-oil.
Fast pyrolysis processes are the most commonly used for
the production of bio-oil. This process converts thermochem-
ically ground particles of biomass into bio-oil. It also produces
bio-charcoal, which can be used as a fertilizer, even in organic
production systems, and many other applications, such as
the prevention of environmental pollution and decontami-
nation of water bodies and soil affected by toxic metals. In
this process, biomass particles with less than 5 mm in diam-
eter are used. These are fed into the system, with the aid of
a carrier gas, at a temperature of 700°C and at high speed,
which can reach 400 m s"^. The flowchart in Fig. 3 shows
the alternatives proposed in this system and the processes
used.
According to Embrapa (2009), the bio-oil yield represents up
to 60 g 100 g"^ (by weight) of the raw material used, i.e., 80001 of
orange residue can yield up to 48001 of bio-oil. The remainder
can be used for charcoal production (Embrapa, 2009). The use
of waste orange (peel and pulp) for energy is of great interest
since every 100 kg of such waste can provide around 27 kg of
charcoal (Tienne et al., 2004). Thus, the 32001 of waste remain-
ing after bio-oil production could be used to produce 8641 of
charcoal.
5.3. Essential oil extraction - System 3
The orange residue (solid and liquid) could be used for the
extraction of essential oils. The solid residues remaining after
the essential oil extraction could be reutilized to obtain cellu-
lolytic fibers which can be used as a support for semi-solid
fermentation, as proposed by Yasar et al. (2007) and Rivas
et al. (2008) or for dietary fiber production (Chau and Huang,
2003; Bortoluzzi and Marangoni, 2006; Bicu and Mustata,
610 FOOD A N D BIOPRODUCTS PROCESSING 9 O ( 2 0 1 2 )
Juice production
T T
8.0001- Solid and liquid waste Solid residues
Extraction
Wet milling
12.81- Essential oils
Drying
Sieving
Dietary Tiber - 5.2001
/ \
Insolubleßber Solubleßber
2.191t 10761
Fig. 4 - Flowchart showing process to extract essential oil
from orange waste.
2011), The liquid residues remaining after the essential oil
extraetion ean be used in eombination with the fibers, as
a substrate for the production of enzymes for semi-solid
fermentation.
The production of essential oils from orange peel is eco-
nomically viable, since this by-product has high added value
(Anagnostopoulou et al,, 2006), Citrus essential oils are used
in a wide variety of applications in the food and pharma-
ceutical industries. They can be used directiy as flavorings
in foods and beverages as well as in the production of
medicines, cosmetics, and cleaning products (Raeissi et al,,
2008),
The maximum extraction yield for citrus oils is 0,4 g 100 g~^,
i,e,, for every ton of fruit processed 4 kg of oil are produced
(Bizzo, 2009), Thus, from the total amount of solid residues
generated in the produetion of juiee (80001) and eonsidering
an extraction process with 40% efficiency, approximately 12,81
of essential oils can be obtained.
Among the many sources of dietary fiber, citrus by-
products have a high potential for use. There has been mueh
interest in the use of the fibers from the peel and dehydrated
membranes. The washed pulp has been demonstrated to be a
good souree of soluble and insoluble dietary fiber and its spe-
eifie teehnologieal funetions and functional properties allow
its use as an ingredient in foods (Marti et al,, 2011), Consid-
ering the solid residue is approximately 70 g 100 g"^ fiber (on
a dry basis) and after drying the fiber shows 7 g 100 g~^ mois-
ture (on a dry basis), the fiber 3neld is 52001, Bortoluzzi and
Marangoni (2006) deseribed a similar proeess, but the fiber
was obtained directly from the dry residue after juice extrae-
tion, and obtained yields of 47,9 g 100g"^ from 20,7 g 100 g"''
insoluble fiber and soluble fiber (Bortoluzzi and Marangoni,
2006),
Carau et al, (2007) studied the antioxidant capacity of
the dietary fiber of orange by-products and it exhibited
high antioxidant capacity, Garcia et al, (2002) showed that
the addition of cereal or fruit fiber, specifically 1,5 g 100 g~i
orange fiber, to dry fermented sausages gives organoleptic
characteristic similar to those of a conventional high fat
product.
In this context, the flowchart in Fig, 4 shows the alterna-
tives proposed in this system and the processes used.
606-614
Juice production
8.0001 Orange waste
T
Drying
T
Dry milling
T
Enzimatic inativation
Filtration Solid residues
Hot water - 120 °C • Extraction
Compost
342 Pectin
Fig. 5 - Flowchart showing proposed process for obtaining
pectin from orange waste.
5.4. Pectin production - System 4
Pectin is a soluble fiber that can be obtained from the
residues of orange processing. It is a natural food additive
used extensively in the food industry. The world market
demand for pectin is in excess of 30,0001 annually and is
growing by around 4-5 g 100 g~^ y~^ (Partos, 2006; Yeoh et al,,
2008),
The industrial process employs extraction of pectin acid
or hydroehlorie sulfurie aeid, whieh generates toxie waste
(Kimball, 1991), Hot water extraction can be considered as an
alternative proeedure for the extraetion of peetin from orange
pulp (Soler, 1995), The idea is to use a proeess that generates
nontoxic waste which can then be utilized. The production of
peetin from the residues of oranges proeessed to juiee has a
yield of approximately 25 g 100 g~^ (on a dry basis) (Kar and
Arslan, 1999), Considering that 80001 of residues are gener-
ated daily and that these residues are submitted to drying
until reaehing 10 g 100 g"^ moisture and that the yield in the
peetin extraction is around 19 g 100 g~^ (Calliari and Gómez,
2004), approximately 3421 of pectin can be obtained. The
remaining solid residue could be used to make compost. The
proposed process to obtain pectin from orange waste is shown
in Fig, 5,
5.5. Solid residue as adsorbent - System 5
Adsorption is a technique which has been used successfully
for the effective removal of heavy metals and chemical com-
pounds from wastewaters generated by the chemical and
textile industries. The first step to an efficient adsorption
process is the ehoiee of an adsorbent with high seleetivity,
high eapaeity and long life. This should also be avail-
able in large quantities at low cost (Pérez-Marín et al,,
2008), According to Ströher (2010), these low-cost adsor-
bents have been investigated in laboratory scale to treat
wastewater with varying degrees of efficiency. An example
of this class of adsorbents is orange pulp, whieh has natural
adsorption eharaeteristies whieh resemble those of aetivated
carbon.
Another alternative for the removal and reeovery of ehem-
ieal compounds from water is by means of adsorption onto
 FOOD A N D BIOPRODUCTS PROCESSING 9 O ( 2 0 1 2 ) 605-614 611

E s;
en Ä
il 2 X X J X

g£
c eu
2 X X X X X

S
o 143
O C
u CI
u XI X X X S X

'S) 2

Sj 00

CO
00
o

.-Hg
3 -a
O" CO

<o S*

u ex
g

o w

3 «

•a Q.S

1 S «S
E *
Mill
ing

Ul X X X X
P. D-
o
•a
2
<u
oo.
CO

.S-P
Bb-g 3-

o
T3
eu
4..I
eu en
ipaji

"co O
D,
COI
an:

X X X X X X
i5 .û
C 2

CJ

en
612 FOOD A N D BIOPRODUCTS PROCESSING
Juice production
8,0001 Orange waste
Milling
To remove adhering
din and soluble
components such as
Washing tannins, resins,
reducing sugar and
colouring agents.
Drying
Adsorbent compounds
Fig. 6 - Flowchart showing proposed process for obtaining
adsorbent material from orange peel.
orange waste gel loaded with zirconium, as proposed by
Biswas et al, (2008), These authors suggested the use of
orange waste immobilized with zirconium (IV) to investigate
its feasibility for phosphate removal from an aquatic envi-
ronment. Using this method, the prepared gel was found to
be an effective adsorbent for phosphate removal with a rea-
sonably high Sorption capacity of 57mg-P/g, whieh is four
times higher than that of zireonium ferrite. The adsorption
capacity has been compared to that of two commercially
available adsorbents: zireonium ferrite and MUROMAC XMC
3614, Fig, 6 presents a method for the production of an
adsorbent of metals and chemical compounds from orange
peel,
5.6. Integrated process for production of ethanol,
biogas and limonene - System 6
An integrated proeess ean be used to produce ethanol, biogas
and limonene from orange wastes. Depending on the mar-
ket and the profitability of the process, pectin can also be
recovered as a by-product of the proeess, Pourbafrani et al,
(2010) suggested the application of this new process to produce
ethanol and biogas and provided a configuration for its indus-
trial application. Their proposal was based on the simplicity
of the proeess and low priée of the biomass eompared to other
ethanol proeesses involving the use of lignocelluloses, making
this process unique and favorable. By applying this proeess,
the same authors found that 39,64 L of ethanol, almost 45 m^
of pure methane, 8,9 L of limonene can be produced per ton of
the wet citrus waste. Fig, 7 shows an adapted flowchart of the
process proposed as an alternative for the complete utiliza-
tion of the waste generated in the orange juiee industry. For
the ealeulation, we considered 80001 of orange waste obtained
from the juice produetion,
5.7. Benefits of the proposed systems
Table 1 shows the proposed systems and their respective
economic benefits, environmental benefits and investments
required, estimated aeeording to literature data and based on
the research by Amante (1997),
6. Final considerations
The orange waste generated by orange juice processing plants
can be reused as a raw material for other industries, adding
9 O ( 2 0 1 2 ) 605-614
Juice production
8,0001 — > • Orange waste
1
Hidrolysis reactor
1 71.200 L
Expansion tank Condenser/deeanter |—>•] Limonene
\ hydrolysaie
solid liquid
Filier
\ 1
Biogas digestor Fermenter
Biogas sUIhse
Dcstilation
344.000 ni^ ;
Ethanol 3I7.200L
Adapted from Pourbafrani et al, (2010)
Fig. 7 - Flowchart showing proposed process for complete
utilization of orange waste.
value to this residue and reducing the microbiological con-
tamination and the environmental pollution as well as the
cost of exploration of natural resources, as mineral bio-oil and
ethanol obtained from non-renewable sourees. The proposals
for uses of the orange waste presented herein may be a initial
step to evaluate the eeonomic feasibility and environmental
impact of the implementation of the proposed systems in the
pilot scale and future industrial application.
Acknowledgments
This paper was first presented at the 2nd International Work-
shop Advances in Cleaner Production (Sao Paulo, May 2009) and
its presentation was assisted by the organizers for whieh we
are grateful.
References
Abecitrus, 2008, Historia da Laranja e Subprodutos da Laranja,
Available from: www,abecitrus,com,br/ (accessed 06,08,08),
Ajmal, M,, Rao, R,A,K,, Ar, A,J,, 2001, Adsorption studies on Citrus
reticula (fruit peel of orange): removal and reeovery of Ni(II)
from electroplating wastewater, J, Hazard, Mater, 79,117-131,
Amante, E,R,, 1997, Proposiçôes metodológicas para a
minimizaçâo de residuos de fecularias e das industrias
processadoras de aves, suinos e pescados do Estado de Santa
Catarina, Tese de Doutorado, Universidade Federal de Santa
Catarina,
Anagnostopoulou, M,A,, Kefalas, P,, Papageorgiou, V,P,,
Assimopoulou, A,N,, Boskou, D,, 2006, Radical scavenging
activity of various extracts and fractions of sweet orange peel
(Citrus sinensis). Food Chem, 94,19-25,
Bicu, I,, Mustata, F,, 2011, Cellulose extraction from orange peel
using sulfite digestion reagents, Bioresour, Technol, 102,
10013-10019,
Biswas, B,k,, Inoue, K,, Ghimire, K,N,, Harada, H,, Ohto, K,,
Kawakita, H,, 2008, Removal and recovery of phosphorus from
water by means of adsorption onto orange waste gel loaded
with zirconium, Bioresour, Technol, 99, 8685-8690,
Bizzo, H,R,, 2009, Óleos essenciais no Brasil: aspectos gérais,
desenvolvimento e perspectivas, Quim, Nova 32 (3), 588-594,
Bortoluzzi, R,C,, Marangoni, C, 2006, Caracterizaçâo da fibra
dietética obtida da extraçâo do suco de laranja. Rev, Bras,
Prod, Agroind, 8 (1), 61-66,
Braddock, R,J,, 1995, By-products of citrus fruit. Food Technol, 49
(9), 74-77,
Calliari, CM,, Cómez, r,J,H,C,, 2004, Extraçào de Pectina de Bagaço
de Laranja [Citrus sinensis] por Acido Cítrico, In: XIX Congresso
 FOOD A N D BIOPRODUCTS PROCESSING 9 0 ( 2 0 1 2 )
Brasileiro de Ciencia e Tecnologia de Alimentos, Recife - PE,
ANAIS.
Chau, C.F, Huang, Y.A., 2003. Comparison of the chemical
composition and physicochemical properties of different
fibers prepared from the peel of Citrus sinensis L. Cu. Liucheng. J.
Agrie. Food Chem. 51, 2615-2618.
Corazza, M.L., Rodrigues, D.G., Nozaki, J., 2001. Preparaçào e
caracterizaçào do vinho de laranja. Quim. Nova 24, 449-452.
Crupi, F., Dugo, P., Di Ciacomo, G., Rispoli, C, Di Giacomo, A.,
2001. Sulla produzione del sueco di arancia in Italia. Parte I.
Essenze Derivati Agr. 71,121-132.
Donsi, F., Annunziata, M., Sessa, M., Ferrari, G., 2011.
Nanoencapsulation of essential oils to enhance their
antimicrobial activity in foods. LWT-Food Sei. Technol. 44,
1908-1914.
Embrapa-Empresa Brasileira de Pesquisa Agropecuaria, 2009.
Relatório de Atividades 2009. Available from:
http://www.cnpae.embrapa.br/publicacoes-para-
download/relatorio-de-atividades-2009/ (accessed
20.10.11).
Faostat, 2010. World census of agriculture. Available from:
http://faostat.fao.org/ (accessed 07.08.10).
Farhat, A., Fabiano-Tixier, A.S., El Maataoui, M., Maingonnat, J.F.,
Romdhane, M., Chemat, F., 2011. Microwave steam diffusion
for extraction of essential oil from orange peel: kinetic data,
extract's global yield and mechanism. Food Chem. 125,
255-261.
Garau, M.C., Simal, S., Rossello, C, Femenia, A., 2007. Effect of
air-drying temperature on physico-chemical properties of
dietary fibre and antioxidant capacity of Orange (Citrus
aurantium v. Canoneta) by-products. Food Chem. 104,
1014-1024.
Garcia, M.L., Dominguez, R., Galvez, M., Gaviez, D., Casas, C,
Selgas, M.D., 2002. Utilisation of cereal and fruit fibres in low
fat dry fermented sausage. Meat Sei. 60, 227-236.
Gareia-Castello, E.M., Mayor, L., Chorques, S., Arguelles, A.,
Vidal-Brotóns, D., Gras, M.L., 2011. Reverse osmosis
concentration of press liquid from orange juice solid wastes:
flux decline mechanisms. J. Food Eng. 106,199-205.
Grohmann, K., Cameron, R.G., Buslig, B.S., 1995. Fraetionation
and pretreatment of orange peel by dilute aeid hydrolysis.
Bioresour. Teehnol. 54,129-141.
Haykiri-Aema, H., Yaman, S., Kueukbayrak, S., 2010. Comparison
of the thermal reaetivities of isolated lignin and holoeellulose
during pyrolysis. Fuel Proeess. Teehnol. 91, 759-764.
Kar, F., Arslan, N., 1999. Effeet of temperature and eoneentration
on viseosity of orange peel peetin solutions and intrinsie
viseosity-molecular weight relationship. Carbohydr. Polym.
40, 277-284.
Kimball, D., 1991. Citrus Proeessing—Quality Control and
Technology. Van Nostrand Reinold, New York.
Mamma, D., Kourtoglou, E., Christakopoulos, P, 2008. Fungal
multienzyme produetion on industrial by-produets of the
eitrus-proeessing industry. Bioresour. Teehnol. 99, 2373-2383.
Marti, N., Saura, D., Fuentes, E., Lizamac, V., Gareia, E.,
Mico-Ballestera, M.J., Lorentea, J., 2011. Fiber from tangerine
juice industry. Ind. Crops Prod. 33, 94-98.
Martin, M.A., Siles, J.A., Chica, A.F., Martín, A., 2010.
Biomethanization of orange peel waste. Bioresour. Teehnol.
101, 8993-8999.
Melèndez-Martinez, A.J., Britton, G., Vieario, I.M., Heredia, F.J.,
2008. The complex carotenoid pattern of orange juices from
concentrate. Food Chem. 109, 546-553.
Mendonça, L.M.V., Conceiçâo, A., Piedade, J., Carvalho, V.D.,
Theodoro, V.C.A., 2006. Caracterizaçào da eomposiçâo quimiea
e do rendimento dos residuos industriáis do limâo Tahiti
(Citrus lati/olia Tanaka). Ciêneia Teenol. Aliment. 26, 870-874.
Moreira, O.S., Reis, R.B., Lana, A.M.Q., 2004. Produçâo e
Composiçâo do leite de Vaeas Alimentadas eom Polpa CitHea
em Substituiçâo ao Milho. Anais da Reuniâo anual da
Soeiedade Brasileira de Zooteenia 41, CD-ROM.
Nighojkar, S., Phanse, Y., Sinha, D., Nighojkar, A., Kumar, A., 2006.
Produetion of polygalaeturonase by immobilized cells of
606-614 613
Aspergiüus niger using orange peel as inducer. Proeess
Bioehem. 41,1136-1140.
Özbay, N., Apaydm-Varol, E., Uzun, B.B., Pütün, A.E., 2008.
Charaeterization of bio-oil obtained from fruit pulp pyrolysis.
Energy 33,1233-1240.
Partos, L, 2006. A first, peetin ingredient enters Cargill's portfolio.
Available from:
http://www.dairyreporter.eom/news/ng.asp?id=61305
(aeeessed 22.08.10).
Pereira, C.L.F., 2008. Avaliaçâo da sustentabilidade ampliada de
produtos agroindustriais. Estudo de easo: suco de laranja e
etanol. Dissertaçào de mestrado. Universidade Estadual de
Campinas - UNICAMP, Campinas, Sao Paulo, Brazil.
Pérez-Madn, A.B., Ballester, A., González, F, Blázquez, M.L.,
Muñoz, J.A., Sáez, J., Zapata, V.M., 2008. Study of cadmium,
zine and lead biosorption by orange wastes using the
subsequent addition method. Bioresour. Teehnol. 99,
8101-8106.
Pourbafrani, M., Forgées, G., Horváth, I.S., Niklasson, C,
Taherzadeh, M.J., 2010. Produetion of biofuels, limonene and
peetin from eitrus wastes. Bioresour. Technol. 101, 4246-4250.
Raeissi, S., Diaz, S., Espinosa, S., Peters, C.J., Brignole, E.A., 2008.
Ethane as an alternative solvent for supercritical extraction of
orange peel oils. J. Supereht. Fluids 45, 306-313.
Reda, S.Y., Leal, E.S., Batista, E.A.C., Barana, A.C., Sehnitzel, E.,
Carneiro, PI.B., 2005. Caraeterizaçâo dos óleos das sementes
de limâo rosa (Citrus ümonia Osbeek) e limâo sieiliano (Citrus
limonon), um residuo agroindustrial. Ciêneia Tecnol. Aliment.
25, 672-676.
Rivas, B., Torrado, A., Torre, P, Converti, A., Dominguez, J.M., 2008.
Submerged eitde aeid fermentation on orange peel
autohydrolysate. J. Agrie. Food Chem. 56, 2380-2387.
Roussos, PA., 2011. Phytoehemieals and antioxidant eapaeity of
orange (Citrus sinensis (1.) Osbeek ev. Salustiana) juiee
produeed under organie and integrated farming system in
Greece. Sei. Hortie. 129, 253-258.
Rutkowski, R., 2011. Pyrolysis of eellulose, xylan and lignin with
the K2CO3 and ZnCb addition for bio-oil produetion. Fuel
Proeess. Teehnol. 92, 517-522.
Siles, J.A., Li, Q., Thompson, 1., 2010. Biorefinery of waste orange
peel. Crit. Rev. Bioteehnol. 30 (1), 63-69.
Soler, M.P, 1995. Frutas-eompotas, doees em massa, geléias e
frutas eristalizadas—manual para a miero e pequeña
empresa. ITAL, Campinas.
Ströher, A.P., 2010. Tratamento por adsorçâo em bagaço de laranja
de um efluente da industria textil. Dissertaçào de mestrado.
Universidade Estadual de Maringá - UEM, Maringá, PR, Brazil.
Tavares, V.B., Siviéri, K., Cerón, C.R., Silva, R., Trabueo, E., 1998.
Utilizaçâo de residuo liquido de industria de proeessamento
de sueo de laranja eomo meio de cultura de Pénicillium
citrinum: depuraçâo biológica do residuo e produçâo de
enzima. Quim. Nova 21, 722-725.
Teixeira, J.C., 2001. Utilizaçâo da polpa eítriea na alimentaçâo de
bovinos leiteiros Parte I. Milkbizz Teenol. 1 (3), 25-28.
Tienne, L., Desehamps, M.C., Andrade, A.M., 2004. Froduçâo de
earvâo e subprodutos da pirólise da easea e do bagaço de
laranja (Citrus sinensis). Rev. Biomassa Energia 1,
191-197.
Tripodo, M.M., Lanuzza, F., Mieali, G., Coppolino, R., Nueita, R,
2004. Citrus waste reeovery: a new environmentally friendly
proeedure to obtain animal feed. Bioresour. Teehnol. 91,
111-115.
Usda, 2010. Edueation and researeh. http://www.usda.gov.
Available from: http://faostat.fao.org/ (aeeessed 07.08.10).
Viuda-Martos, M., Ruiz-Navajas, Y., Fernández-López, J.,
Perez-Alvarez, J., 2008. Antifungal aetivity of lemon (Citrus
lemon L.), mandarin (Citrus reticulata L.), grapefruit (Citrus
paradisi L.) and orange (Citrus sinensis L.) essential oils. Food
Control 19,1130-1138.
Widmer, W., Zhou, W., Grohmann, K., 2010. Pretreatment effeets
on orange proeessing waste for making ethanol by
simultaneous saeeharifieation and fermentation. Bioresour.
Teehnol. 101, 5242-5249.
614 POOD A N D BIOPRODUCTS PROCESSING 9 O ( 2 0 1 2 ) 606-614

Wilkins, M,R,, Suryawati, L,, Maness, N,0,, Chrz, D,, 2007a,
Ethanol production by Saccharomyces cereuisiae and
Kluyueromyces marxianus in the presence of orange-peel oil,
World J, Microbiol, Biotechnol, 23,1161-1168,
Wilkins, M,R,, Widmer, WW, Crohmann, K,, 2007b, Simultaneous
saccharification and fermentation of citrus peel waste by
Saccharomyces cereuisiae to produce ethanol. Process Biochem,
42,1614-1619,
Yasar, F,, Togrul, H,, Arslan, N,, 2007, Flow properties of cellulose
and carboxymethyl cellulose from orange peel, J, Food Eng, 81,
187-199,
Yeoh, S,, Shi, J,, Langrish, T,A,C,, 2008, Comparisons between
different techniques for water-based extraction of
pectin from orange peels. Desalination 218, 229-237,
Copyright of Food & Bioproducts Processing: Transactions of the Institution of Chemical Engineers Part C is
the property of Elsevier Science and its content may not be copied or emailed to multiple sites or posted to a
listserv without the copyright holder's express written permission. However, users may print, download, or
email articles for individual use.