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Short Communication
a r t i c l e
i n f o
Article history:
Received 16 November 2009
Received in revised form 14 January 2010
Accepted 20 January 2010
Available online 9 February 2010
Keywords:
Citrus waste
Ethanol
Biogas
Limonene
Pectin
a b s t r a c t
Production of ethanol, biogas, pectin and limonene from citrus wastes (CWs) by an integrated process
was investigated. CWs were hydrolyzed by dilute-acid process in a pilot plant reactor equipped with
an explosive drainage. Hydrolysis variables including temperature and residence time were optimized
by applying a central composite rotatable experimental design (CCRD). The best sugar yield (0.41 g/g
of the total dry CWs) was obtained by dilute-acid hydrolysis at 150 C and 6 min residence time. At this
condition, high solubilization of pectin present in the CWs was obtained, and 77.6% of total pectin content
of CWs could be recovered by solvent recovery. Degree of esterication and ash content of produced pectin were 63.7% and 4.23%, respectively. In addition, the limonene of the CWs was effectively removed
through ashing of the hydrolyzates into an expansion tank. The sugars present in the hydrolyzates were
converted to ethanol using bakers yeast, while an ethanol yield of 0.43 g/g of the fermentable sugars was
obtained. Then, the stillage and the remaining solid materials of the hydrolyzed CWs were anaerobically
digested to obtain biogas. In summary, one ton of CWs with 20% dry weight resulted in 39.64 l ethanol,
45 m3 methane, 8.9 l limonene, and 38.8 kg pectin.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
World production of citrus fruits is over 88 million tons per year
(Marin et al., 2007). Almost half of these fruits is squeezed to juice,
and the remainder including peel, segment membranes and other
by-products is considered as citrus wastes (CWs) (Wilkins et al.,
2007a). These CWs can be dried and used as raw material for pectin
extraction or pelletized for animal feed (Mamma et al., 2008).
However, a large fraction of CWs is still deposited every year. This
deposition is not favored due to both economic and environmental
arguments such as high transportation costs, lack of disposal sites,
and the land-lling material having high organic content (Tripodo
et al., 2004).
CWs contain different carbohydrate polymers, which makes
them interesting sources for production of biogas and ethanol
(Gunaseelan, 2004; Mizuki et al., 1990; Pourbafrani et al., 2007;
Wilkins et al., 2007b). The main obstacle to using CWs as a substrate for biogas production is the presence of limonene in CWs.
This component is very toxic for digesting microorganisms and decreases the biogas yield (Mizuki et al., 1990). Limonene is also a
A process based on dilute-acid hydrolysis of CWs can be considered as another alternative (Grohmann et al., 1995; Talebnia et al.,
2008). However, the data are limited to the lab-scale experiments
and it is difcult to scale up the process to industrial scale. In both
studies (Grohmann et al., 1995; Talebnia et al., 2008), mechanical
pretreatment was used before hydrolysis and the experiments
were carried out in low solid/liquid ratio (Grohmann et al.,
1995). Furthermore, dilute-acid hydrolysis showed low yields of
sugars from the carbohydrate polymers.
The aim of the current work was to introduce a new process for
production of ethanol and biogas from CWs. The CW was pretreated with dilute-acid explosion process to hydrolyze the CWs
and also to get rid of limonene. The resultant slurry was then centrifuged, and the liquid part was fermented to ethanol and distilled.
The stillage from the distillation column and the remained solids
were mixed and digested to biogas. An industrial conguration
was suggested for this process.
2. Methods
2.1. Citrus wastes composition
The CWs used in this work was the residue of orange obtained
from Brmhults juice factory (Bors, Sweden) and stored frozen at
20 C until use. Total dry content of CW was determined by drying at 110 C for 48 h and it was 20.00 0.80% w/w. The composition of the CWs used in this work as percentage of dry matter was:
glucose 8.10 0.46; fructose 12.00 0.21; sucrose 2.80 0.15; pectin 25.00 1.20; protein 6.07 0.10; cellulose 22.00 1.95; hemicellulose 11.09 0.21; ash 3.73 0.20; lignin 2.19 0.04 and
limonene 3.78 0.30.
2.2. Dilute-acid hydrolysis
A 10-L high-pressure reactor (Process & Industriteknik AB, Sweden) was used for dilute-acid hydrolysis. The CWs was diluted with
distilled water to obtain 2 kg slurry with 15% total solid content.
Sulfuric acid (98%) was added to the slurries to reach nal concentration of 0.5% v/v. The slurries were then hydrolyzed at various
temperatures of 130, 150 or 170 C with different residence times
of 3, 6 and 9 min according to the experimental design (Table 1). A
central composite rotatable design (CCRD) was used to design the
experimental setup and to optimize hydrolysis variables including
temperature and time (Talebnia et al., 2008). The reactor was
heated with direct injection of 60-bar steam, provided by a power
Table 1
Experimental design of hydrolysis temperature and time in dilute-acid hydrolysis of
CWs and the total sugars yield of each hydrolysis (actual and predicted values based
on the model in Eq. (1)).
Test no.
1
2
3
4
5
6
7
8
9
10
11
12
13
a
Variables
YTSa
YTSa
T (C)
Time (min)
Actual
Predicted
130
170
130
170
130
170
150
150
150
150
150
150
150
3
3
9
9
6
6
3
9
6
6
6
6
6
26.49
33.73
30.41
33.00
28.60
36.85
35.65
37.55
42.05
40.54
41.09
41.58
41.40
25.38
33.73
29.40
33.10
30.71
36.74
36.75
38.45
40.93
40.93
40.93
40.93
40.93
4247
4248
The hydrolyzed CWs was supplemented with nutrients and fermented anaerobically by bakers yeast. The concentration of different sugars prior to inoculation was 15.17, 10.88, 2.91 and 4.01 g/l
for glucose, fructose, galactose and arabinose, respectively. The
yeast strain was not able to ferment arabinose, but it could assimilate the hexoses. The fermentation was completed in 24 h, in
which all the fermentable sugars were consumed and ethanol
was produced. Ethanol yield based on total fermentable sugar consumption was 0.43 0.02 g/g. Glycerol, biomass and succinic acid
were the identied by-products, which had yields of 0.10 0.01,
0.070 0.008 and 0.0060 0.0004 g/g, respectively. The carbon
balance in the fermentation was 1.02 0.03.
The citrus wastes from orange juice production were hydrolyzed with 0.5% v/v sulfuric acid at 130170 C for 39 min, and
the results are summarized in Table 1. The maximum sugar yield,
42.05%, was achieved at 150 C and 6 min. However, the more realistic value is the average of results of the 9th to 13th experiments
(Table 1), with a sugar yield value of 41.33 0.56%. Increasing the
temperature and time to more than their optimal values results in
a decrease of the total liberated sugars (Table. 1). This is most likely
due to decomposition of hexose sugars (mainly fructose) to
hydroxymethylfurfural (Grohmann et al., 1995; Talebnia et al.,
2008). A second order mathematical model was tted to obtained
sugar yields:
2
4249
Citrus Waste
Sulfuric Acid
Water
Hydrolysis Reactor
Steam
Expansion Tank
Condenser/Decanter
Limonene
Hydrolysate
Solid
Liquid
Filter
Biogas Digester
Biogas
Precipitator
Pectin Depleted
Residue
Fermenter
Pectin
Dryer
Dried Pectin
Ethanol
Distillation
Stillage
Fig. 1. Block ow diagram for production of ethanol, biogas, pectin and limonene from CW.
4250
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