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116 Chiang Mai J. Sci. 2008; 35(1)

Chiang Mai J. Sci. 2008; 35(1) : 116-122

www.science.cmu.ac.th/journal-science/josci.html
Contributed Paper

Value Added Products from By-products of Rice Bran

Oil Processing
Wasinee Kaewboonnum, Ketmanee Wachararuji and Artiwan Shotipruk*
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330,
Thailand.
*Author for correspondence; e-mail: artiwan.sh@chula.ac.th

Received : 17 October 2007

Accepted : 30 October 2007

ABSTRACT
This study deals with the production of value-added product derived from rice
bran oil processing by-products. The investigation was divided into two parts, Part I: subcritical
water (SW) hydrolysis of deoiled rice bran and Part II: separation of from rice
bran oil soapstock. In Part I SW hydrolysis reaction was carried out in a closed batch reactor
in which the effect of temperature in the range of 200-220 oC, reaction time of 10-30 min,
raw material to water weight ratio of 1:5 and 2:5, were determined on the of protein, amino
acid, reducing sugars, and antioxidant activity. The results in the present study suggested that
subcritical water could be used to potentially hydrolyze deoiled rice bran into more valuable
products. The suitable condition for protein and amino acids production from deoiled rice
bran by subcritical water hydrolysis was 1:5 at 30 min and hydrolysis temperature of 220 oC.
At this condition, the protein: 130.17 mg/g rice bran, amino acid: 9.14 mg/g rice bran. In Part
II, separation of from rice bran oil soapstock was conducted following the selected
processes from literatures. The processes involve saponification, dehydration, leaching and
crystallization. The content of was analyzed by using UV spectrophotometer. The
selected processes were demonstrated as suitable means for separating from
soapstock obtained locally.

Keywords: Subcritical water, rice bran oil, deoiled rice bran, soapstock, .

1. INTRODUCTION
Rice is a major agricultural product of . Currently, rice bran is mostly used
Thailand with annual productivity of about as animal feed (60%), while the rest (40%) is
29 million tons due to suitable topography used to produce value added edible cooking
and climate nature [1]. Commonly, consumers oil. Although rice oil is considered nutritious
prefer white rice therefore brown rice is oil and is becoming popular especially in USA
subjected to milling process. Rice bran is an and Europe, during rice bran oil processing,
important by product of the milling process a large amount of bran nutrition was lost
which is enriched with fibre, proteins, oil, and along with the by products. Here we are
important antioxidants such as vitamin E and interested in two major by products of the
Chiang Mai J. Sci. 2008; 35(1) 117

rice oil processing: deoiled bran and soapstock. separation of from domestic
Deoiled bran is rich in proteins and amino soapstock.
acid and is obtained after oil extraction. In this study we divided our investigation
Soapstock is obtained after deacidification by into two parts. Part I: Subcritical water
alkali treatment of crude rice bran oil during hydrolysis of deoiled rice bran and Part II:
the refining process. It has a significant amount Separation of from rice bran oil
of , which is an important soapstock.
component that shows many health benefits
such as reduction of cholesterol in the blood 2. MATERIAL AND METHOD
and anti-aging effect etc. At present, the Part I: Subcritical water hydrolysis of
majority of both deoiled bran and soapstock deoiled rice bran
is used as animal feed. The objective of this 2.1.1 Materials. Deoiled rice bran was
study is therefore to increase the value of these obtained from Thai Edible Oil Co., Ltd.,
by products. Ayuthaya, Thailand.
Generally, proteins and amino acid that 2.1.2 Subcritical water hydrolysis. The
are presented in deoiled bran can be extracted hydrolysis reaction was carried out in
by chemical method which is alkai or acid closed batch reactor in which the effect of
hydrolysis, followed by acid precipitation. temperature in the range 200-220 oC, reaction
However, low protein yield was obtained due time of 10-30 min and raw material to water
to degradation at extreme pH condition. weight ratio of 1:5 and 2:5 on the yield of
Alternatively, enzymatic process has been protein, amino acid and reducing sugar.
studied but the process takes a long time and 2.1.3 Analytical method
the high cost of enzymes make the process 1) Analysis of protein. Protein content
commercially uneconomical. Subcritical water of soluble portion was assayed using Lowry’s
or pressurized water at the temperature method [3], using bovine serum albumin
between boiling point (100 oC) and its critical (BSA) as a standard.
temperature (374.15 oC) is an interesting 2) Analysis of amino acids. Amino acids
alternative. At such condition, water polarity content was analyzed by Ninhydrin assays
decreases, thus make it better solvent for using L-Glutamic acid as a standard.
extraction of several organic bioactive 3) Analysis of reducing sugar. Reducing
substances. sugars content was assayed by dinitrosalicylic
Separations of from rice colorimetric method, using D-Glucose as a
bran oil soapstock have been investigated for standard using dinitrosalicylic reagent
many decades. In the development of these developed by Sumner (1921) [4].
processes into commercial scale, several 4) ABTS.+scavenging assay. ABTS (2,2’-
factors such as productivity, environmental azinobis-(3-ethylbenzothiazoline-6-sulfonic
and health concerns, process investment, and acid) radical cation scavenging assay was
separation efficiency (purity and yield) carried out following a modified method
must be considered. Furthermore, isolation described by Re et al., 1999 [5]. For comparing
procedure developed for one soapstock the antioxidant activity of the extracts obtained
does not necessarily work well with another at various conditions, concentration of sample
soapstock [2]. Consequently, in this study, we producing 50% reduction of the radical
employed selected processes from literatures absorbance (IC50) was used as an index. The
and further investigated the experimental IC50 values for various extracts were found
118 Chiang Mai J. Sci. 2008; 35(1)

from the plots of percent inhibition (PI) versus dehydration, leaching, and crystallization.
the corresponding concentration of the 2.2.3 Quantification of
sample. The values of PI were calculated using contents was deter mined by
the following equation: spectrophotometric method.

PI (%) = [1-(At /Ar)] x 100 3. RESULTS AND DISCUSSIONS

where At and Ar are absorbance of test sample Part 1: Subcritical water hydrolysis of
and absorbance of the reference, respectively. deoiled rice bran
3.1.1 Protein of soluble products
Part II: Separation of from rice The amounts of protein in the soluble
bran oil soapstock products obtained by SW hydrolysis of
2.2.1 Materials Rice bran oil soapstock was deoiled rice bran at various conditions are
obtained from Thai Edible Oil Co., Ltd., shown in Figure 1. The highest protein (130.17
Ayuthaya, Thailand. + 2.48 mg/g deoiled rice bran) was obtained
2.2.2 Separation of The selected from the 220 oC hydrolysis for 30 min. Based
processes [6, 7, 8] were applied to separate on the amount in the original bran reported
from soapstock. This process by NIR (15.53 %wt ) this account for the
includes the following steps: saponification, protein recovery of 84%.

Figure 1. Protein yield after hydrolysis of deoiled rice bran at different temperature and time.

3.1.2 Amino acid of soluble product

The amino acids of soluble products than the amino acid production. The
obtained at various hydrolysis conditions are temperature and reaction time do not have
shown in Figure 2. The highest yield was 9.74 significant effects on the amount of total
50.08 μg/g raw rice bran, which was amino acids. At this condition, the result
obtained at 220 oC for 20 min. This relatively indicated that the rate of amino acid
low yield indicates that the rate of amino acids production was comparable to the rate of
decomposition to smaller molecules of amino acid decomposition into smaller
organic acids or other products was faster organic acids.
Chiang Mai J. Sci. 2008; 35(1) 119

Figure 2. Amino acid yield after hydrolysis of raw materials at different temperature and
time

3.1.3 Reducing sugar in soluble products for the hydrolysis product obtained at 220oC
When carbohydrate reacts with and 30 min, whose reducing sugar content
hydronium and hydroxide ions, reducing decreased. This result again indicated that at
sugars are produced. The reducing sugar of this condition, the rate of reducing sugar
the soluble hydrolysis products at different decomposition into smaller molecules of
temperature and time are shown in Figure 3. organic carbon was high, and that the
The reducing sugar content in the soluble decomposition of reducing sugar to other
products increased with increasing product was favored over the production of
temperatures and times of reaction, except reducing sugar.

Figure 3. Reducing sugar yield after hydrolysis of raw materials at different temperature and
time
120 Chiang Mai J. Sci. 2008; 35(1)

3.1.4 Effect of ratio of raw material-to-

water on extraction yield water was increased from 1:5 to 2:5. This is
The effect of the ratio of raw material- mainly because the high content of raw
to-water on extraction yield was studied by material increases the density and viscosity of
comparing the product obtained from two the mixture, therefore caused the poor mixing
different ratios of deoiled rice bran-to-water, of raw material and water, thus mass transfer
1:5 and 2:5 for reaction conditions at 210 oC decreased and the accessibility of water to
and 30 min (Figure 4). It was found that the particles of raw materials was difficult. The
of protein, amino acids and reducing sugar ratio of raw material-to-water of 1:5 was
decreased when the ratio of raw material-to- therefore more suitable.

Figure 4. Effect of ratio of deoiled rice bran-to-water (1:5 and 2:5) for 210 oC and 30 min

3.1.5 Antioxidant activity

In this study, the antioxidant activity of min, antioxidant activity increased as
soluble products obtained with SW was temperature increased from 200oC to 220oC.
evaluated with ABTS •+ scavenging assay. For the reaction time of 30 min, however,
Antioxidant activity was represented by (IC50) the antioxidant activity only increased slightly
index which is the concentration of sample or stayed constant with the increase in
producing 50% reduction of the radical temperature. The increase in water tempera-
absorbance. The antioxidant activity was ture not only increases the ion product which
measured at hydrolysis temperature of 200oC causes hydrolysis reaction but also causes the
and 220 oC and hydrolysis time at 20 min and breakdown of hydrogen bonds. Hydrogen
30 min. These conditions were found bonds of water keep the water molecules
to be suitable and were selected for the together, thus separating themselves from
antioxidatant test. The results in Figure 5 other organic compounds. When the H-bonds
indicated that with the hydrolysis time of 20 breakdown, several antioxidative organic
Chiang Mai J. Sci. 2008; 35(1) 121

compounds within the rice bran and soybean thus the activity might decrease [8]. It is
samples were better able to dissolve in water, recommended that in the future study,
thus the soluble products exhibited higher analysis should be carried out to identify the
antioxidant activity. At long exposure time antioxidant compounds obtained in the
with high temperature, however, some soluble products.
antioxidative compounds might be degraded,

Figure 5. Antioxidant activity (IC50) of the soluble products at hydrolysis times of 20 and 30
min and temperature of 200 oC and 220 oC.

Figure 6. Spectrum peak scanning report for sample comparable to standard.

(a) standard, (b) sample.
122 Chiang Mai J. Sci. 2008; 35(1)

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