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 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614

Contents lists available at SciVerse ScienceDirect

Food and Bioproducts Processing

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

Review

Proposals for the residues recovery: Orange waste as raw

material for new products

K. Rezzadori a , S. Benedetti a , E.R. Amante b,∗

a Department of Chemical and Food Engineering, Federal University of Santa Catarina, EQA/CTC/UFSC, 88040-900 Florianópolis, SC,
Brazil
b Department of Food Science and Technology, Center of Agricultural Science, Federal University of 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 tons y−1 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, hemicellulose, 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: [email protected] (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.org/10.1016/j.fbp.2012.06.002
 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614 607

1. Introduction Orange

Orange is a citrus fruit consumed in high quantities all over Reception

the world in the natural and peeled forms and as a juice. It
Selection
is associated with a low cost and contains many nutrients
including vitamin C, A and B, minerals (calcium, phosphorus, Cleaning Rejected orange Composting
potassium), dietary fiber and many phytochemicals, includ-
50 % juice Juice extraction Orange waste Reuse
ing flavonoids, amino acids, triterpenes, phenolic acids and
carotenoids (Melèndez-Martínez et al., 2008; Roussos, 2011)
Filtration
Oranges are one of the most important commodities in 45,5 % 0,5 %
solid waste liquid waste
terms of global agricultural production, ranked in 20th posi- Pasteurization
tion in 2008 and representing around 10.5% of the world fruit
production (Faostat, 2010; Usda, 2010). Brazil is responsible for Blending
around 53% of the orange juice produced worldwide and for
Freezing packing
80% of the international trade in this product (Abecitrus, 2008).
According to Faostat, in 2009 the Brazilian orange production
Storage/Shipping
was almost 18 million tons, representing approximately 49%
of the total fruit production in this country. Fig. 1 – Flowchart showing orange juice process.
During orange juice production, only around the half of the
fresh orange weight is transformed into juice (Braddock, 1995),
in products with high added value obtained through chemical
generating great amounts of residue (peel, pulp, seeds, orange
or enzymatic hydrolysis and subsequent biological conversion
leaves and whole orange fruits that do not reach the quality
(Rivas et al., 2008).
requirements), which accounts for the other 50% of the weight
The soluble sugars present in orange peel are glucose, fruc-
of the fruit and has a moisture content of approximately 82 g
tose, and sucrose. The insoluble polysaccharides of the cellular
100 g−1 (Abecitrus, 2008; Garcia-Castello et al., 2011). This huge
wall of the orange peel are composed of pectin, cellulose, and
amount of waste is, in most cases, spread on soil in areas
hemicelluloses. Pectin and hemicelluloses are rich in galac-
adjacent to the production locations, for its final use as a raw
turonic acid, arabinose, and galactose, and also contain small
material in animal feed, or else it is burned (Martín et al.,
amounts of xylose, rhamnose and glucose (Grohmann et al.,
2010). This method of waste handling produces highly pol-
1995).
luted wastewater in terms of chemical and biological oxygen
After the extraction of juice from the oranges, the peel,
values which can negatively affect the soil and the ground and
seeds, and pulp are usually transformed into pelletized bran
superficial waters (Braddock, 1995).
for animal feed. Among the liquid residues spilled into the
One alternative to improve the management of these
environment the residue known as “yellow water” is of major
residues is the implementation of new processes for their
concern since it has a high content of organic matter, making
recovery, for instance, through the production of organic
it an agent with high pollution potential (Tavares et al., 1998).
fertilizers, pectin, bio-oil, essential oils, and antioxidant com-
Some by-products of the citrus industry have expressive com-
pounds, or as a substrate for the production of several
mercial value: the essential oils obtained from orange peel are
compounds with high added value, such as microbial pro-
notable for their use as ingredients in foods, beverages, cos-
teins, organic acids, ethanol, enzymes and biologically active
metics and perfumes, aromatic essences; d-limonene is used
secondary metabolites and adsorbent materials. These are
in the production of inks and solvents; the bran of citric pulp
excellent alternatives to avoid environmental pollution and
is employed in the production of animal feed; and orange pulp
to add value to these substances (Abecitrus, 2008).
is used by the food and beverage industries (Pereira, 2008). The
Due to the great amount of residues generated at orange
industrial processing of orange juice is detailed in Fig. 1.
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 3. Proposals for the use of orange waste
solid and liquid residues. Also, the levels of economic invest-
ment required and the benefits available to industries able to A vast number of promising proposals for the use of orange
process this waste and increase its value are discussed, along waste have been described in the literature. These include the
with the environmental issues. The results are presented in use of the waste to produce fertilizer, essential oils, pectin,
the form of a review, contemplating the waste characteriza- ethanol, industrial enzymes, single cell proteins, pollutant
tion and alternative uses of this material, information which absorbents and paper pulp supplements (Siles et al., 2010).
is then used as a basis for calculating the volumes generated In the search for alternative solutions to the problems asso-
in an orange juice processing company. 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
2. Residue characterization: orange waste toxic compounds. Anaerobic digestion, in which both pollu-
tion control and energy recovery can be achieved, is another
The valorization of residues requires knowledge of their chem- possible way to treat and add value to the abundant orange
ical composition. Orange waste contains 16.9 g 100 g−1 soluble peel waste. This process is defined as the biological conversion
sugars, 9.21 g 100 g−1 cellulose, 10.5 g 100 g−1 hemicelluloses, of organic material to a variety of end products including ‘bio-
and 42.5 g 100 g−1 pectin, which is its most important compo- gas’ whose main constituents are methane (65–70 g 100 g−1 )
nent. Due to its composition being rich in soluble and insoluble and carbon dioxide. Martín et al. (2010) have shown that the
carbohydrates, this by-product shows great potential for use anaerobic digestion of orange peel waste after a d-limonene
608 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614

extraction reveals higher methane production, providing an microwave. Farhat et al. (2011) studied a new process for the
excellent opportunity to integrate this waste into orange juice extraction of essential oil from orange peel called microwave
manufacturing using a biorefinery approach. steam diffusion and concluded that it is an efficient method
Agroindustrial residues, such as those generated in citric for the extraction of essential oil from orange peel, providing
juice production plants, have also been used as a substrate for good yields.
the production of enzymes. Nighojkar et al. (2006) studied the The application of alternative materials in the adsorp-
use of orange peel as a substrate and inducer in the production tion of chemical compounds and toxic metals present in
of polygalacturonase by microorganisms and concluded that industrial effluents, particularly in research laboratories, are
orange peel is a very good inducer. Mamma et al. (2008) con- scarce; however, some studies have shown that this strat-
cluded that it is possible to produce pectinolytic, cellulolytic egy has potential. As an example, it has been demonstrated
and xylanolytic enzymes from the fungal strains of the genera that orange pulp is effective for removing heavy metals from
Aspergillus, Fusarium, Neurospora and Penicillium and generate industrial effluents. According to Ajmal et al. (2001), the use of
multienzyme activity using a simple growth medium con- orange bagasse as an alternative adsorbent is effective in the
sisting of a solid by-product of the citrus processing industry removal of Ni from electroplating effluent, where more than
(orange peel). 93% of the metal was adsorbed. Pérez-Marín et al. (2008) eval-
These residues also have high energy value, and they can uated the use of orange waste in the biosorption of cadmium,
help to reduce the dependency on energy purchased for the zinc and lead and obtained good results. Biswas et al. (2008)
generation of heat, vapor, or electricity. Despite the great studied the removal and recovery of phosphorus from water
opportunities for the use of such residues, there are few exam- by means of adsorption onto an orange waste gel loaded with
ples in the literature of the application of residues from the zirconium and concluded that it is a promising and potentially
orange agro-industry for energy generating purposes, either attractive adsorbent for treating wastewater contaminated
in the form in which they are produced or after their trans- with inorganic phosphate and consequently provides a step
formation (Widmer et al., 2010). Before they are used in the towards a sustainable society.
generation of thermal energy, the solid residues from oranges The bran of citric pulp, or orange peel bran, is another
can be converted into charcoal and into the by-products of very important by-product. This bran is obtained through the
carbonization, which would widen their range of uses and treatment of solid residues and liquid remaining after juice
at the same time facilitate their transportation, storage, and extraction. The pelletized bran of citric pulp is used as a com-
handling. According to Tienne et al. (2004), the pyrolysis of plement in animal feed, and is well accepted as an ingredient
orange peel is possible based on the gravimetric income asso- in bovine feed (Corazza et al., 2001). The use of industrial
ciated with the coal and carbon obtained and concluded that residues derived from citric fruits in animal diets reflects the
the charcoal production and utilization of the by-products importance of fibers in the maintenance of the ruminal motil-
from the pyrolysis of peel and orange pulp allow value to ity and also to motivate rumination. However, this fiber needs
be added to this agroindustrial residue. In addition, the pulp to be in the appropriate condition. It has been emphatically
fruit can be used for bio-oil production also employing pyrol- stated that the use of fiber in human nutrition is correlated
ysis (Özbay et al., 2008). According to Embrapa (2009), orange with the prevention of diseases (Mendonça et al., 2006).
waste is a good biomass for bio-oil production, yielding up
to 60 g 100 g−1 by weight compared to the raw material used, 4. Case study
i.e., a ton of solid residue can yield up to 600 kg of bio-oil
(Embrapa, 2009).
The quantitative data on the residues generated by the orange
The citrus processing waste can be used to produce
processing industry were obtained from the literature and
ethanol, limonene, and other co-products. Extensive work has
from information supplied by a local orange juice production
been carried out with enzymatic hydrolysis to liquefy this
plant. The proposals to increase the value of the orange waste
residue and maximize the monomeric sugar content. These
will be presented as flowcharts, mass balances and yields for
sugars can be subsequently or simultaneously (Wilkins et al.,
each system, based on calculations and production data relat-
2007a,b) converted into ethanol by fermentation. Widmer et al.
ing to a large orange juice plant with a daily processing rate of
(2010) studied the use of citrus processing waste for ethanol
approximately 16,000 t. This production will be considered to
production by saccharification and fermentation processes
estimate both the amount of solid and liquid waste processed
and observed that the ethanol yields based on the sugar
and the derivatives produced.
content after enzymatic hydrolysis following 48 h of simul-
taneous saccharification and fermentation ranged from 76%
to 94%.
5. New products from orange waste:
Another quite profitable alternative for the residues gen-
proposals and yields
erated during orange processing is the extraction of essential
oils, that is, volatile oils extracted from the citric fruit peel The characteristics of solid and liquid orange residues suggest
(Donsì et al., 2011). These essential oils have several applica- that these waste materials can be used for the development
tions in the pharmaceutical and food industries. d-Limonene of new products. This paper proposes six products which
is an oily fraction and it is considered to be one of the purest can be obtained from the solid fraction and four from the
sources of monocyclic terpene (Corazza et al., 2001; Viuda- liquid fraction of the orange waste. The company under
Martos et al., 2008). Also, these oils can contain compounds study produces 8000 t day−1 of pasteurized and concentrated
with biological activity, such as limonoids and their gluco- juice, using 16,000 t day−1 of oranges, with the generation of
sides, which cause the inhibition of cancerous tumors induced 8000 t day−1 of orange waste (considering 50% of the raw mate-
in rats, mice, and hamsters (Reda et al., 2005). Various tech- rial).
niques can be used for the extraction of essential oil, such The alternatives are presented as systems for the use of
as supercritical extraction, hydrodistillation, distillation and residues from the orange juice industry.
 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614 609

Juice production Juice production

8,000 t Solid residue 8,000 t Solid residue

Hot gas
power generation
Pressing methods chemical and/or Milling
enzymatic
Gas-liquid separation
Drying Drying

carrier gas Downflow reactor

7,200 t Citric pulp 700 °C
Bio-oil 4,800 t
864 t Charcoal
Pelletized

Fig. 3 – Flowchart showing process involved in bio-oil and

Storage/Shipping
charcoal production.

Fig. 2 – Flowchart detailing the process involved in the use

Although research in this area is still in the initial stages, bio-
of orange peel for animal feed.
oil has great potential to replace petroleum, with advantages
in various applications. The bio-oil is a renewable organic fuel
5.1. Production of ingredients for animal feed – System derived from the processing of agricultural and forest residues.
1 It is a black oil with a characteristic odor and high perfor-
mance and can be obtained not only from pyrolysis but also
Solid waste generated during orange juice production can be thermal degradation (Embrapa, 2009). Bio-oils may be used
used to produce ingredients for animal feed (fresh or dried for many applications for example as a transport fuel or as
orange pulp). This system includes the most common proce- an additive to conventional fuels and to feedstock chemicals.
dures applied by orange juice production plants regarding the According to Haykiri-Acma et al. (2010) and Rutkowski (2011),
destination of the residues. Most plants make use of almost the biomass used as an energy source is mainly a mixture
all the residue generated in the industrial process for the pro- of three main components, i.e., cellulose, hemicellulose and
duction of animal feed (Moreira et al., 2004). lignin. Due to the high content of these components in the
The dried pulp it is obtained after two pressings (which orange waste, the residue generated from orange juice pro-
reduces the moisture content to 65–75 g 100 g−1 ) and drying duction is considered a good biomass for the production of
(resulting in up to 90 g 100 g−1 dry matter), before being pel- bio-oil.
letized and marketed (Teixeira, 2001). According to the same Fast pyrolysis processes are the most commonly used for
author, to facilitate the separation of the water and lessen the production of bio-oil. This process converts thermochem-
the hydrophilic nature of the pectin, the main carbohydrate ically ground particles of biomass into bio-oil. It also produces
present in the pulp, calcium hydroxide or calcium oxide is bio-charcoal, which can be used as a fertilizer, even in organic
added before the pressings. Due to the high water content in production systems, and many other applications, such as
the fresh pulp it is difficult to dry in common industrial drying the prevention of environmental pollution and decontami-
devices, while its high content of organic matter means that nation of water bodies and soil affected by toxic metals. In
it cannot be disposed of easily (Crupi et al., 2001). However, this process, biomass particles with less than 5 mm in diam-
there are chemical and/or enzymatic methods available that eter are used. These are fed into the system, with the aid of
facilitate the pressing of this waste and reduce its water con- a carrier gas, at a temperature of 700 ◦ C and at high speed,
tent sufficiently to permit it to be dried in a normal industrial which can reach 400 m s−1 . The flowchart in Fig. 3 shows
drier (Tripodo et al., 2004). the alternatives proposed in this system and the processes
As shown in Fig. 2, the solid orange waste obtained could used.
be used as an ingredient for animal feed due to the high con- According to Embrapa (2009), the bio-oil yield represents up
tent of sugars, fiber and other residual substances. According to 60 g 100 g−1 (by weight) of the raw material used, i.e., 8000 t of
to data found in the literature, in the production of orange orange residue can yield up to 4800 t of bio-oil. The remainder
juice the residues correspond to 50% of the raw material. can be used for charcoal production (Embrapa, 2009). The use
Therefore, since the processing plant investigated in this case of waste orange (peel and pulp) for energy is of great interest
processes 16,000 t of oranges day−1 , around 8000 t of solid since every 100 kg of such waste can provide around 27 kg of
and liquid residues are generated daily. Considering that the charcoal (Tienne et al., 2004). Thus, the 3200 t of waste remain-
liquid residue (“yellow water”) corresponds to 0.5 g 100 g−1 ing after bio-oil production could be used to produce 864 t of
(by weight) of the total residue, 40 t of liquid residues and charcoal.
7960 t of solid residues are generated daily at this plant.
Considering that the feed produced from that residue has 5.3. Essential oil extraction – System 3
10 g 100 g−1 moisture, from 8000 t of solid residues 7200 t of
bran can be obtained daily and used as an ingredient for The orange residue (solid and liquid) could be used for the
animal feed. extraction of essential oils. The solid residues remaining after
the essential oil extraction could be reutilized to obtain cellu-
5.2. Bio-oil and charcoal production – System 2 lolytic fibers which can be used as a support for semi-solid
fermentation, as proposed by Yasar et al. (2007) and Rivas
Currently, the pyrolysis of biomass is of particular interest et al. (2008) or for dietary fiber production (Chau and Huang,
as a means to produce bio-oil, which is a valuable product. 2003; Bortoluzzi and Marangoni, 2006; Bicu and Mustata,
610 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614

Juice production Juice production

8,000 t Solid and liquid waste Solid residues 8,000 t Orange waste

Extraction Drying
Wet milling
12.8 t Essential oils
Dry milling
Drying

Sieving Enzimatic inativation

Dietary fiber 5,200 t Filtration Solid residues

Hot water - 120 °C Extraction

Insoluble fiber Soluble fiber Compost
2,491 t 1,076 t 342 t Pectin

Fig. 4 – Flowchart showing process to extract essential oil

Fig. 5 – Flowchart showing proposed process for obtaining
from orange waste.
pectin from orange waste.

2011). The liquid residues remaining after the essential oil 5.4. Pectin production – System 4
extraction can be used in combination with the fibers, as
a substrate for the production of enzymes for semi-solid Pectin is a soluble fiber that can be obtained from the
fermentation. residues of orange processing. It is a natural food additive
The production of essential oils from orange peel is eco- used extensively in the food industry. The world market
nomically viable, since this by-product has high added value demand for pectin is in excess of 30,000 t annually and is
(Anagnostopoulou et al., 2006). Citrus essential oils are used growing by around 4–5 g 100 g−1 y−1 (Partos, 2006; Yeoh et al.,
in a wide variety of applications in the food and pharma- 2008).
ceutical industries. They can be used directly as flavorings The industrial process employs extraction of pectin acid
in foods and beverages as well as in the production of or hydrochloric sulfuric acid, which generates toxic waste
medicines, cosmetics, and cleaning products (Raeissi et al., (Kimball, 1991). Hot water extraction can be considered as an
2008). alternative procedure for the extraction of pectin from orange
The maximum extraction yield for citrus oils is 0.4 g 100 g−1 , pulp (Soler, 1995). The idea is to use a process that generates
i.e., for every ton of fruit processed 4 kg of oil are produced nontoxic waste which can then be utilized. The production of
(Bizzo, 2009). Thus, from the total amount of solid residues pectin from the residues of oranges processed to juice has a
generated in the production of juice (8000 t) and considering yield of approximately 25 g 100 g−1 (on a dry basis) (Kar and
an extraction process with 40% efficiency, approximately 12.8 t Arslan, 1999). Considering that 8000 t of residues are gener-
of essential oils can be obtained. ated daily and that these residues are submitted to drying
Among the many sources of dietary fiber, citrus by- until reaching 10 g 100 g−1 moisture and that the yield in the
products have a high potential for use. There has been much pectin extraction is around 19 g 100 g−1 (Calliari and Gómez,
interest in the use of the fibers from the peel and dehydrated 2004), approximately 342 t of pectin can be obtained. The
membranes. The washed pulp has been demonstrated to be a remaining solid residue could be used to make compost. The
good source of soluble and insoluble dietary fiber and its spe- proposed process to obtain pectin from orange waste is shown
cific technological functions and functional properties allow in Fig. 5.
its use as an ingredient in foods (Martí et al., 2011). Consid-
ering the solid residue is approximately 70 g 100 g−1 fiber (on 5.5. Solid residue as adsorbent – System 5
a dry basis) and after drying the fiber shows 7 g 100 g−1 mois-
ture (on a dry basis), the fiber yield is 5200 t. Bortoluzzi and Adsorption is a technique which has been used successfully
Marangoni (2006) described a similar process, but the fiber for the effective removal of heavy metals and chemical com-
was obtained directly from the dry residue after juice extrac- pounds from wastewaters generated by the chemical and
tion, and obtained yields of 47.9 g 100 g−1 from 20.7 g 100 g−1 textile industries. The first step to an efficient adsorption
insoluble fiber and soluble fiber (Bortoluzzi and Marangoni, process is the choice of an adsorbent with high selectivity,
2006). high capacity and long life. This should also be avail-
Garau et al. (2007) studied the antioxidant capacity of able in large quantities at low cost (Pérez-Marín et al.,
the dietary fiber of orange by-products and it exhibited 2008). According to Ströher (2010), these low-cost adsor-
high antioxidant capacity. Garcia et al. (2002) showed that bents have been investigated in laboratory scale to treat
the addition of cereal or fruit fiber, specifically 1.5 g 100 g−1 wastewater with varying degrees of efficiency. An example
orange fiber, to dry fermented sausages gives organoleptic of this class of adsorbents is orange pulp, which has natural
characteristic similar to those of a conventional high fat adsorption characteristics which resemble those of activated
product. carbon.
In this context, the flowchart in Fig. 4 shows the alterna- Another alternative for the removal and recovery of chem-
tives proposed in this system and the processes used. ical compounds from water is by means of adsorption onto
Table 1 – Systems for the processing of residues generated by the orange juice industry.
Systems Original Original Operations involved
solid liquid
residue residue

Press- Mill- Dry- Pyro- Com- Gas liquid Siev- Pellet- Wash- Fermen- Filtr- Extrac- Distill- Hydro-

food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614

ing ing ing lysis post separation ing ized ing tation ation tion ation lysis

1 x x x x x
2 x x x x x x
3 x x x x x x
4 x x x x x x x
5 x x x x
6 x x x x x x x

Systems Purposes Economic Environmental Investment

benefit benefit involved

Ingredient for Charcoal Fiber Bio-oil Adsorbent Essential oils Biogas Ethanol Pectin
animal feed or
compost

1 x L M L
2 x x H H M
3 x x H H H
4 x x H H H
5 x x M H L
6 x x x x H H H

Economic benefit: Low: L < cost of the conventional treatment of residues; Medium: M ≤ 5 × cost of the conventional treatment of residues; High: H > 5 × cost of the conventional treatment of residues.
Environmental benefit: Low: L − environmental evaluation parameters are reduced by up to 60%; Medium: M − environmental evaluation parameters are reduced by 60–90%; High: H − environmental evaluation
parameters are reduced over 90%.
Investment involved: Low: L − investment in the installation of the system of up to US$ 500,000; Medium: M − investment in the installation of the system of US$ 500,000–1,000,000; High: H − investment in the
installation of the system of over US$ 1,000,000.

611
612 food and bioproducts processing 9 0 ( 2 0 1 2 ) 606–614

Juice production Juice production

8,000 t Orange waste

8,000 t Orange waste
Hidrolysis reactor
71,200 L
Milling
To remove adhering Expansion tank Condenser/decanter Limonene
dirt and soluble
hydrolysate
components such as solid li q u id
Washing tannins, resins, Filter
reducing sugar and
colouring agents. Biogas digestor Fermenter
Drying
stillage
Biogas Destilation

344,000 m3
Adsorbent compounds Ethanol 317,200 L

Fig. 6 – Flowchart showing proposed process for obtaining

Adapted from Pourbafrani et al. (2010)
adsorbent material from orange peel.
Fig. 7 – Flowchart showing proposed process for complete
orange waste gel loaded with zirconium, as proposed by utilization of orange waste.
Biswas et al. (2008). These authors suggested the use of
orange waste immobilized with zirconium (IV) to investigate value to this residue and reducing the microbiological con-
its feasibility for phosphate removal from an aquatic envi- tamination and the environmental pollution as well as the
ronment. Using this method, the prepared gel was found to cost of exploration of natural resources, as mineral bio-oil and
be an effective adsorbent for phosphate removal with a rea- ethanol obtained from non-renewable sources. The proposals
sonably high sorption capacity of 57 mg-P/g, which is four for uses of the orange waste presented herein may be a initial
times higher than that of zirconium ferrite. The adsorption step to evaluate the economic feasibility and environmental
capacity has been compared to that of two commercially impact of the implementation of the proposed systems in the
available adsorbents: zirconium ferrite and MUROMAC XMC pilot scale and future industrial application.
3614. Fig. 6 presents a method for the production of an
adsorbent of metals and chemical compounds from orange Acknowledgments
peel.
This paper was first presented at the 2nd International Work-
5.6. Integrated process for production of ethanol, shop Advances in Cleaner Production (São Paulo, May 2009) and
biogas and limonene – System 6 its presentation was assisted by the organizers for which we
are grateful.
An integrated process can be used to produce ethanol, biogas
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