Ruj . Kami Tarikh

UNIVERSITI SAINS MALAYSIA--

2008/074 (U0060) : 9 September 2011

Prof. Ir. Mohd. Omar Ab. Kadir Pusat Pengajian Teknologi Industri Universiti Sains Malaysia 11800 USM PULAU PINANG

Tuan,

I Pejabat Pengurusan Dan Kreativiti Penvelidil<an Research Creativity and Management Office

Canselori,

Universiti Sains Malaysia Aras 6, Bangunan Canselori 11800, USM Pu lau Pi nang T : (6)04-65331 08/3178/3988/5019 F : (6)04-6566466/8470

: (6)04-653 2350

L : www.resea rch.usm.my

LAPORAN AKHIR GERAN PENYELIDIKAN UNIVERSITI PENYELIDIKAN (RU) TAJUK PROJEK : ENHANCING OIL YIELD AND OPTIMIZATION OF OIL MEDIUM CHAIN

TRIGL YCERIDES (MCTS) CONTENT IN SUPERCRITICAL CARBON DIOXIDE EXTRACTION OF COCONUT OIL FROM FRESH COCONUT (Cocos nucifera L.)

NO. AKAUN 1001 1 PTEKIND 181401 3

Dengan hormatnya perkara di atas dirujuk.

2. Terlebih dahulu saya ucapkan terima kasih atas penghantaran laporan akhir Geran RU seperti tajuk di atas. Bersama-sama ini dilampirkan komen penilaian daripada Dekan Penyelidikan Pelantar Kejuruteraan & Teknologi untuk perhatian tuan.

3. Memandangkan projek ini telah selesai, Pejabat ini akan menutup projek ini dan seterusnya pihak Jabatan Bendahari diminta untuk memproses penutupan akaun projek ini selepas semua urusan tuntutan dan bayaran dalam tempoh projek dijalankan diselesaikan.

4. Selanjutnya, tuan diminta untuk mengambil tindakan seperti dinyatakan di bawah :

a) Merakamkan penghargaan kepada Universiti Sains Malaysia. Sila pastikan nama Universiti ditulis/ditaip dengan penuh/lengkap iaitu 'Universit i Sains Malaysia'.

b) Tiga salinan penerbitan berkaitan mesti dikirimkan ke Bahagian Penyelidikan dan Inovasi untuk tindakan selanjutnya.

c) USM mempunyai opsyen pertama untuk menerbitkan bahan yang dihasilkan melalui projek ini. Ini akan dilakukan melalui Penerbit USM dan keputusan untuk menerbitkan bahan ini akan dibuat dalam tempoh enam bulan.

d) Bahagian ini akan mengagihkan semula peralatan yang telah dibeli menggunakan peruntukan geran ini seandainya terdapat penyelidik lain yang memerlukan peralatan tersebut.

5. Bahagian ini mengucapkan tahniah di atas kejayaan tuan selaku Ketua Penyelidik menyelesaikan projek dengan jayanya. Tuan akan dihubungi oleh Pejabat Inovasi untuk perkembangan selanjutnya has ii/outcome daripada geran ini sekiranya terdapat harta intelek/pengkomersialan hasil geran yang boleh diketengahkan.

Sekian, terima kasih .

"BERKHIDMAT UNTUK NEGARA" 'Memastikan Kelestarian Hari Esok'

(HAZL~N ABDU L HA ) Ketua Penolong Pendaftar Pejabat Pengurusan & Kreativiti Penyelidikan Bahagian Penyelidikan & Invovasi

--bAPORAN AKHIR-GERAN PENYELIDIKAN tJNIVERSITI PENYELIDIKAN (RU) TAJUK PROJEK : ENHANCING OIL YIELD AND OPTIMIZATION OF OIL MEDIUM CHAIN

TRIGL YCERIDES (MCTS) CONTENT IN SUPERCRITICAL CARBON DIOXIDE EXTRACTION OF COCONUT OIL FROM FRESH COCONUT (COCONUT NUCIFERA L.)

NO. AKAUN 1001 / PTEKIND 1814013

s.k. Dekan Penyelidikan Pelantar Kejuruteraan & Teknologi Pejabat Pelantar Penyelidikan USM Kampus Kejuruteraan

Dekan Pusat Pengajian Teknologi Industri Universiti Sa ins Malaysia

Pengarah Pejabat Inovasi Universiti Sains Malaysia

Timbalan Dekan (Pengajian Siswazah & Penyelidikan) Pusat Pengajian Teknologi Industri Universiti Sa ins Malaysia

Ketua Pustakawan r)"'::;;~Perpustakaan Hamzah Sendut ~Universiti Sains Malaysia

HAH/aihat

Ketua Penolong Sendahari Seksyen Kewangan Penyelidikan Jabatan Sendahari Universiti Sains Malaysia

Pegawai Sains Pelantar Kejuruteraan & Teknologi Pejabat Pelantar Penyelidikan USM Kampus Kejuruteraan

Laporan Akhir - MohdOmarAbKadir (U0060)

} }

Disampaikan satu salinan laporan akhir projek untuk simpanan Perpustakaan

Sila ambil tindakan menutup akaun projek dan kemukakan satu salinan penyata kewangan terakhir ke Sahag ian ini

=

UNIVERSITI SAINS MALAYSIA

UNIVERSITY RESEARCH G FINAL REPORT 0)-

Geran Penyelidikan Univ Laporan Akhir

A. PARTICULARS OF RESEARCH I MAKLUMAT PENYELJDIKAN:

(i) Title of Research: Tajuk Penyelidikan: Enhancing Oil Yield & Optimization of Oil Medium Chain Triglycerides ( MCTs) Contents in Supercritical Carbon Dioxide Extraction of Coconut Oil from Fresh Coconut (Cocos nucifera L)

(ii) Account Number: Nombor Akaun: 10011PTEKINDI814013

B. PERSONAL PARTICULARS OF RESEARCHER / MAKLUMA T PENYELIDIK:

(i) Name of Research Leader: Nama Ketua Penyelidik:Prof Mohd Omar Ab Kadir

Name of Co-Researcher Nama Penyelidik Bersama: Prof. Dr Nik Norulaini Nik Ab. Rahman

En. Wahyu B. Setianto En. Abu Hanipah Nawi

(ii) Schoolllnstitute/Centre/Unit Pusat Pengajian IlnstitutlPusatlUnit : Pusat Pengajian Teknologi Industri

C. Research Platform (Please tick (/) the appropriate box): Pelantar Penyelidikan (Sila tanda (I) kotak berkenaan):

D A. Life Sciences Sains Hayat

D B. Fundamental Fundamental

D C. Engineering & Technology Kejuruteraan & Teknologi

D D. SQcial Transformation Transformasi Sosial

D E. Information & Communications Technology (ICT) Teknologi Maklumat & Komunikasi

D F. Clinical Sciences Sains Klinikal

D G. Biomedical & Health Sciences Bioperubatan Sains Kesihatan

© Division of Research & Innovation - Unjversi'ti Sains Malaysia - Mal'eh 201 0

D. Duration of this research: Tempoh m?Isa penyelidikan ini :

*DUration: =-:-:-3 tanun ..... = ..... . Tempol? :

From Dari:

Oktober 2007

E. ABSTRACT OF RESEARCH

To Ke:

September 2010

(An abstract of between 100 and 200 words must be prepared in Bahasa Malaysia and in English. This abstract will be included in the Annual Report of the Research and Innovation Section at a later date as a means of presenting the project findings of the researcherls to the University and the community at large)

Abstrak Penyelidikan (Perlu dised iakan di antara 100 - 200 perkataan di dalam Bahasa Malaysia dan juga Bahasa lnggeris . Abstrak ini akan dimuatkan dalam Laporan Tahunan Sahagian Penyelidikan & Inovasi sebagai satu cara untuk menyampaikan dapatan projek tuan/puan kepada pihak Universiti & masyarakat luar).

Minyak kelapa yang disari dari isi kelapa segar dikenali sebagai minyak kelapa dara

(l\I.lKD). Minyak kelapa dara adalah sumber semulajadi trigliserida rantai sederhana (IRS) yang

mana telah dikenali sebagai minyak sihat. Sehingga ke hari ini, penyelidikan berkaitan penyarian

l\IlI<D menggunakan karbon dioksida lampau genting (C02- LG) dari segi dasar pengekstrakkan

masih lagi kurang. Objektif kajian ini adalah untuk menentukan kesan faktor-faktor pengekstrakan

l\IlI<D menggunakan (C02- LG), dan mengkaji keterlarutan minyak tersebut dalam (C02- LG) .

Penilaian kesan-kesan interaksi bagi parameter pengekstrakan telah dilakukan

menggunakan Kaedah Iindakbalas Permukaan (RSlVI). Kajian ini telah dijalankan berdasarkan

reka bentuk Box-Behnken. Iekanan (20.7 - 34.5 MPa), suhu (313 - 353 K) dan jumlah

penggunaan karbon dioksida (10 - 60 g) telah dipilih sebagai parameter. Respon yang terlibat

adalah hasil pengekstrakan dan kandungan IRS dalam minyak yang diekstrak. Hasil

pengekstrakan dikira melalui kaedah gravimetrik dan analisis kandungan IRS dilakukan

menggunakan analisis gas kromatografi (GC). Satu hubungkait telah dibangunkan dengan p -

value untuk kedua-dua respon pada 95% aras keyakinan. Pengukuran keterlarutan dijalankan

menggunakan kaedah dinamik pada julat tekanan dari 20.7 hingga 34.5 :NlPa dan suhu dari 313

© Di vision of Research & Innovation - Uni versiti Sains Malaysia - March 2010

hingga 353 K. Analisis keterlarutan minyak dilakukan secara gravimetrik dan analisis lengkung.

Keterlarutan minyak meningkat dengan suhu pada tekanan di antara 31.0 dan 34.5 IvIPa dan

berkurang dengan suhu pada tekanan di antara 20 .7 dan 24.1 MPa. Data keterlarutan yang

diperolehi daripada eksperimen dikolerasikan menggunakan model Chrastil dan del valle-

Aguilera iaitu berdasarkan ketumpatan karbon dioksida (C02). Keterlarutan kawasan-lintasan

boleh diperhatikan dalam julat tekanan 27.5 hingga 30.5 Mpa dan pada sekitar 29 MPa, yang

menunjukkan keterlarutan MKD dalam CO2- LG tidak dipengaruhi oleh suhu secara praktikalnya.

Kesahihan data keterlarutan telah dilakukan melalui perbandingan dengan data keterlarutan

trigliserida tulen dalam CO2- LG yang pernah dilaporkan dan ujian ketekalan-diri dilakukan

dengan kaedah lvJendez-Santiago dan Teja.

***

Coconut (Cocos nucifera) oil which is extracted from fresh coconut flesh is known as

virgin coconut oil (YCO). The oil is a natural source of medium chain tryglycerides (MCTs)

which has been well known as healthy oil. It is remarkable that very few reports on the extraction

of the YCO using SC-C02 have been published hitherto the fundamental insights on the SC-C02

extraction processes of the coconut oil are much lacking. The objectives of this work are

evaluating the parameters etTects of YCO extraction using SC-C02 and examination of the oil

solubility in SC-C02.

The assessment of interaction effects of extraction parameters was performed using a

Response surface methodology (RSM). The study was carried out according to Box-Behnken

design. Pressure (20.7 - 34.5 MPa), temperature (313 - 353 K) and CO2 consumption (10 - 60 g)

were chosen as the parameters. _The responses were the extraction yield and the MGT s content of

extracted oil. The yield was calculated by gravimetric and the MCTs content analysis "vas

performed using GC analysis. A correlation was established with p -value for both responses at

I 95% confident level. The Solubility meaS1..1rement was performed by dynamic method at the

© Division of Research & Innovation - Universiti Sains Malays ia - M;u'ch 20 I 0

pressures and temperatures range of 20.7 to 34.5 NIPa and 313 to 353 K respectively. Oil

solubility analysis was performed using gravimetric and curve analysis. The' oil solubility

Increases with temperature at pressures between 31.0 and 34.5 MPa and decreases with

temperature at pressures between 20.7 and 24.1 MPa. The solubility experimental data obtained

was correlated with Chrastil and del Valle-Aguilera model, which are based on the C02 density. A

solubility cross-over region was observed in the pressure range of27.5 to 30.5 MPa and at around

29 MPa, the solubility ofVCO in SC-C02 is practically independent of temperature. The validity

of the solubility data was performed by its comparison with previous reported data of pure

triglyceride solubility in SC-C02 and performing a self-consistency test with the method of

Mendez-Santiago and Teja.

F. SUMMARY OF RESEARCH FINDINGS Ringkasan dapatan Projek Penyefidikan

The extraction of coconut oil was performed using SC-C02 at various pressures, temperatures and CO2 consumption levels. This process can successfully be performed, and extracting about 99% ofthe total oil. The extraction yield and the MCTs content of the extracted oil varied with the extraction conditions. A mathematical model based on statistical analysis was established. The correlation between the extraction conditions and the extraction yield as well as the MCTs content applied in this study may be remarkable and should be considered for scaling­up the VCO extraction process.

Solubility of virgin coconut oil (VCO) in supercritical carbon dioxide was examined with a dynamic method. The solubility data could be well-correlated with a density based model. The oil­CO2 system exhibited a cross-over region that could be described by the density based model. The solubility data validation confirms its reliability. The comparison of the solubility of pure triglycerides in SC-C02 with the measured VCO solubilities shows that the latest value are intermediate to lighter and heavier triglycerides solubility in SC-C02 that was reported in the literatures. The data examination using the self-consistency test proposed by Mendez-Santiago and Teja resulted that the data was consistent.

(9 .oi vi sion of R~searcb & Innovation - U ni versiti Sains Mala ys ia - March 20 to

1----1

G. COMPREHENSIVE TECHNICAL REPORT Laporan TeknikaJ Lengk8(J Applicants are required to prepare a comj:lrehensive technical report explainingJhe project. (This report must be attached separately) Siia secjiakan laporan teknika! lengkap yan~l rnenerangkan keseluf'u!wfl projek inL [laporan ini mesH dikepilkanj

Please see attachment.

List the key words that reflectour research: Senarai/(an kata kunci yang mencerminkan penyelicfikan andcl.

English Bahasa Malaysia Virgin coconut oil Minyak kelapa muda

Medium chain triglycerides Rantai trigliserida sederhana

Supercritical CO2 Takat genting CO2

© Division of RcS"IU'C iJ & innovation - Un iversiti Sa ins Malaysia - March 20 10

-

H a) Results/Benefits of this research Hasil Penyelidikan

No. - Category/Number: --- -Bil: Kqtegoril Bilangan:

Promised Achieved

Research Publications

1. (Specify target journals) 3 Penerbitan Penyelidikan (Nyatakan sasaran jurnal)

2. Human Capital Development ,

a. Ph. D Students 1 b. Masters Students 1 c. Undergraduates (Final Year

Project) d. Research Officers 2 e. Research Assisstants 2 f. Other: Please specify

3. Patents Paten -

Developing of new extractor system using a

new view cell and

Specific / Potential Applications repa iring of the old others 4.

SpesifiklPotensi aplikasin system part (High pressure pump and

chiller) . The system also suitable for clinical waste

sterilization.

Networking & Linkages Japan counterpart (Toyo 5. Koatsu) and local Jaringan & Jalinan

counterpart (Sime Darby) Possible External Research Grants

6. to be Acquired Sime Darby group (RM Jangkaan Geran Penyelidikan Luar 3.9 Million) - (potentia l) Diperoleh

• Kindly provide copies/evidence for Category 1 to 6 .

b) Equipment used for this research. Perala tan yang telah digunakan dalam penye/idikan ini.

Items Perkara Approved Equipment Approved Requested Equipment Location

Specialized Extractor with view window Lab 131, Tingkat 1, Equipment

Gas flow meter Bangunan G07, Pusat

Peralatan Pengajian Tek. Ind. , USM khusus High pressure valve Penang.

modification Facility -Kemudahan

Infrastructure Infrastruktur

~ Please attach append ix if necessary .

:\) Division of Research & [nl1ovatiol1 - Uni versiti Sains Malaysia - March 20 10

. -

I. BUDGET f BAJET

Total Approved Budget --I--~I--rotal Additionai Budget--- -

Grand Total of Approved Budget

Total Expenditure

Balance

: RM 257,450.00

:RM -

: RM 257, 450.00

Yearly Budget Distributed

Year 1 :RM122,100.00

Year 2 : RM 91,350.00

Year 3 : RM 44,000.00

Additional Budget Approved

Year 1 : RM

Year 2 : RM

Year 3 : RM

: RM 259,912.77

: RM -3 ,107.21 (deficit)

• Please attach final account statement from Treasury

Signature of Researcher ~~-~:randatan§an Penyelidik

Professor Ir. Moh. Omar Ab. Kadlr, Ph I) $chooloftndustriaJTechn~y

Universiti Sains Malaysia 11800 Penanq

5-4-2011

Date Tarikh

(9 Div.is.ion ofR~search & lnnovation - Uni versiti Sains Malaysia - March 2010

H. COMMENTS OF PT J'S RESEARCH COMMITTEE KOMEN JAWATANKUASA PENYELIDIKAN PERINGKAT PT J

General Comments : Ulasan Umum:

········e·' .......... .- ...... ... ... ;. ........... .................... ·· ·· ···········:·· :······ ····· ·············n·········· ... .... ;.- .. ... ~ .. : ......... ..... .

e~ Csz-OC/L ~ ~ "" tVO ~__ _ ~...,J2--( ( cL k... . •••••• • ••••••••••• ----: •••••• ~ •••• ••• ••••• •• •••••• •••••• •• •• ••• ••• ••••• •••••• •• ••••• ••• •• •••• •••••••• ••. ••••• •••••••••• •• 0:..:.1 ••••••• ••• •••••• ••• ••• •••• •••••••• •

..... .... ~j.~~'3 ... .. .. ... ~.~4:\\.~ .. ~~J~ ..... .. .. ~.~ .......... ?l::)~~{!.f-

. .....r~\i"l; \:P.~ ..... ..... ~~ ... .. .. ~"'?. 3 .... .. ~"""jJ.:..:+.:±:::f.' h

Prcfes"T ?'l\13r " a t F~' ~'a Tim b[1 1an lJekan

Pe n gaj ian S iswa'lah & : (, ~yelid.ika~ P u sat Pen gaj ian Tekn"lcg1 In,ci ustIl

Universiti Sains MalaYSia 11800 Pulau Pinang

Signatu d Sta Chairperson of PT J's Evaluation Committee Tandatangan dan Cop Pengerusi Jawatankuasa Penilaian PT J

Date : ..... t.~ ... /t..(?C!..f ( Tarikh : .. .... ... ..................... ... .... .. ......... . .

Signature and Stamp of Dean! Director of PT J

;;;;:taT:;!y7(Deka~/~engarah PT J P rcSOR ROZM/~N HJ. DIN

DEKAN PUSAT PENGAJIAN TEKNOLOGI INDUSTRI

11 800, USM. PENANG

(9 Division ofRl!search & Innovation - ti ll iversiti Sains Malays ia - M;u'ch 20 10

G. COMPREHENSIVE TECHNICAL REPORT Laporan TekniJ<al LengJ<.ap

Effects of Extraction ParametersonYield and Medium-Chain Triglycerides (MCTs) Content

Qualitative analysis of the sample was performed using GC-MS. The sequence of the peak for all fatty acids which existed in the extracted oil was confirmed by performing GC-MS analysis. Peak scan analysis using MS was performed to indentify the peah. The analysis showed that fatty acid elution depended on the fatty acids molecular weight. Lighter fatty acids (lower molecular weights) were eluted first, followed by the heavier fatty acids .

Spectrophotometric analysis gave the following identification: time (minutes) 1.02; 147; 2. 31 ; 4.38; 7.69; 1147; 15 .61 ; 1599; 16.85 are n-Hexane (solvent for analysis); caprylic acid methyl ester; capric acid methyl ester; lauric acid methyl ester; myristic acid methyl ester; palmitic acid methyl ester; linoleic acid methyl ester; oleic acid methyl ester; stearic acid methyl ester respectively.

As discussed previously, fatty acids that were obtained in the extracted oil were caprylic (C8 :0), capric (CI0 :0), lauric (C1 2:0), myristic (C14:0), palmitic (C16:0), linoleic (C18 :2), oleic acid (C18: 1) and stearic acid (CI8 :0). The target compounds of the extraction were the MCTs. MCTs content ofthe extracted oil were defined as the medium fatty acid (C8:0 - C12 :0) present in the oil.

To determine the effects of interactions between the parameters (pressure, temperature and CO2 consumption) to the extraction yield and the MCTs content of the extracted oil, the response surface methodology (RSM), a statistical analysis was applied (Palma and Taylor, 1999, Myers and lVIontgomery, 2002) . The experimental data were obtained, according to the response surface methodology RSM experiment design as given in Table 1.1.

The design of experiment (DOE) was performed according to Box-Behnken design. Throughout the RSM analysis the unit of temperature was expressed in degree celcius CC).

Table 1.1 : Experimental Program and Results of The Box-Behnken Design of Extraction

Yield and Extracted Oil MCTs Content in The Extraction Using SC-C02 .

Pressure Temperature CO2 Yield

MCTs

Standard consumption content

order (MPa) (0C) (g) (Weight %) (weight %)

( Xl) ( x2 ) (X3 )

1 20.7 40 35 94. 56 5947

2 34.5 40 35 96.25 57.99

.., 20.7 80 35 40 .29 67 27 j

© Di vision of Research & [llnovatioll - Uni vers iti Sains Malays ia - March 20 10

4 34.5 80 35 99.4-1 59.07

5 20.7 60 10 30.21 65.49

6 34.5 60 10 93.37 62.00

7 20.7 60 60 92.37 60.39

8 34.5 60 60 99.08 56.71

9 27.6 40 10 73.69 62.40

10 27.6 80 10 63 .30 64.27

11 27.6 40 60 95.64 58.94

12 27.6 80 60 99.32 58.07

13 27.6 60 35 98.28 59.12

14 27.6 60 35 97.30 59.49

15 27.6 60 35 97.08 56.76

16 27.6 60 35 97.64 56.35

17 27.6 60 35 96.55 56.35

A second-order polynomial model was applied to express the responses as a function of the chosen variables.

y, represents the dependent variables (extracted yield and the IvICTs content), Xs

represents the independent variables (pressure, temperature and CO2 consumption) and bs represents the coefficients. Multiple regression analysis was performed to determine

the regression coefficients of the model (Table 1.2).

Table 1.2 : Estimated Coefficients of Second-Order Response Models for SC-C02

Extraction ofVCO.

intercept

Extraction yield

(%)

-77.2497

9.9870

Extracted oil MCTs content

(%)

88.4694

-1.6310

~_ Di vision of Research &. [nnovation - Ulliversiti SaiJ]s \lIaJaysia - NJaJ'ch 20 J 0

-~--..........-~-. ~'fmi<: _

x1 -1.9022 -0.0206

x_ 3.4872 -0 .2067 J

XI XI -0 .1993 0.0374

.1: 2 .1: 2 -0.0131 0.0039

X3X3 -0.0146 0.0028

X1X2 0.1040 -0.0122

X1X3 -0 .0818 -0.0003

X2X3 0.0070 -0.0014

The effects of pressure, temperature and CO2 consumption on extraction yield and MCTs content can be seen in the sample graph (Figure 1.6). In Figure 1.6a, it was observed that at pressures lower than 28.3 "NIPa, the extraction yield decreased with increase in temperature, while at higher pressures (greater than 28.3 l\1Pa), the yield increased with temperature. This was most likely due to the solubility cross-over phenomenon, which often occurs in solute-C02 systems. The phenomenon is discussed in the section of solubility examination.

Figure 1.6b shows a contour plot of the interaction of the pressure and the CO2

consumption. It is clear that the increase in CO2 consumption resulted in an increase in the yield. At a constant temperature (60 QC) and certain CO2 consumption level, increasing pressure provided higher extraction yields (Fig. 1.6a. The MCTs content increased with increasing temperature, while it decreased with increasing pressure (Fig. 1.6c). The increase in CO2 consumption reduced the MCTs content of the extracted oil (Fig. 1.6d) . The trend of the MCTs content was contrary to that of the yield. This might be due to the shorter chain triglycerides that were extracted more easily than the longer chain triglycerides; consequently, the oil extracted earlier in the process has a higher MCTs content than the fractions extracted later.

(9 Division of R.:search & Innovat ion - Universiti Sains Malaysia - M:u'ch 20 10

'""

Yie ld (%)~~ ~~-60,---~--------~====--~

Yield (%) 80.-~~--~~,-~--,---~

70 48 0 ~ .!:!! ~ "'0 :J (J) +'

~ 60 CfJ

35 :J (1) N

0. 0 E 0 (1)

I-

50 23

40 10

21 24 28 31 35 21 24 28 31 35

Pressure (MPa) Pressure (MPa)

(a) (b)

80 MCTs content (%) MCTs content (%)

60

70 48 0 ~

~ 2.? :J "0

"§ 60 (1) (/) 35 ::l (1)

0. '" E 0 (1) 0 I-

50 23

40~----,L----.-----,-L-~

21 24 28 31 35 21 24 28 31 35 Pressure (MPa) Pressure (MPa)

(c) (d)

Figure L 6 :~ftects of parameters on yield and NIGT-s content of extracted oil. (a) Effects

of pressure and temperature on extraction yield using 35 g CO2 . (b) Effects of pressure

and CO2 consumption on extraction yield at 60°C. ( c) Effects of pressure and

temperature on extracted oil MCTs content using 35 g CO2. (d) Effects of pressure and

CO2 consumption on oil MCTs content at 60 0c.

© Division of R~searcb & InlJova tion - U lli versili Sains Malaysia - Mru'eh 2010

The analysis of variance (ANOVA) for the extraction yield and the extracted oil MCTs content is shown in Table 4.3. The calculated values of F were compared to the

tal51e vruue of 0. p- l.n-p.a) . The ANOVA shows that the calculated value of F for the

yield response (20.52) and that of the MCTs content response (6.44) were greater than the

table (experimental) value of F (09,7,005) = 3.68). If the calculated value of F exceeds

the table value of F , the null hypothesis is rejected at the level of significance, and it is inferred that the coefficient estimates are not all zero (that is, one or more coefficients convey information about the model) and the variation verified that the model is significantly greater than the unexplained variation (noise) (Wonnacott and Wonnacot, 1990). Therefore, the p -value for the yield and the MCTs content responses is below 0.05 . Accordingly, it could be constmed that, at the 95% contldence level, the models were significant for both of the responses. The value of R2 measures the total variation of the observed values about the mean determined by the fitted model. The values of R2 for the yield and the MCTs content responses were 0.96 and 0.90, respectively; hence, the R2 value in this study signifies a good correlation between the experimental data and the predicted values. Therefore, the fitted model obtained can be used to describe the effects of the factors within the experimental ranges.

Table 1.3 : Analysis of Variance (ANOVA) for Extraction Yield and Extracted Oil MCTs

Content.

Extraction Yield

Source

Regression Residual Total

Degrees of freedom

9 7 16

Extracted Oil .MCTs Content

Source Degrees of freedom

Regression 9 Residual 7 Total 16

Sum of squares

7140.38 270.59 7410.98

Sum of squares

151.84 18.33

170.17

Mean Square

793.38 38.66

Mean Square

16.87 2. 62

© Division of R esearch & Innovation - Univcrsiti Sains Malavsia - Mm'ch 2010

0.0.05)

20. 52 0.96 3.68

F R2 0.0.05)

6.44 0.90 3.68

.J

NAMA PRO..EK :

JABATAN BEND.AHA.1.. SUB KUMP WANG UNIV PENYELIDIKAN (1001)

PENYATA PERBELANJAAN P ADA 30 SEPTEMBER 2010 i : ---1 :) I;;J~!:i~CI ~§...9H-. YtEbQ.6NQ9E1JMJ~~DQi'f.QE_QL~MEQl!,I~tQ:!A!N..1B!\,'>!_'!':.C~R.iQ.Ei? (MCTS) CONTENT iN SUPERCRiTiCAL CAR80N DiOXIDE EXiRACTiON OF COCONuT OiL FROM FRES TEMPOH : ' . . ..,

KETUA PRO.EK : PROFESOR MOHO OMAR AS KADIR

j PUSAT PENGAJAN TEKNOLOGI INOUSTRI

_ ____ ---L _ _ ------------ ------ --------- -_."--- -.. . __ .- --- .-----J

- --. - _._---

r I

--~--'

Al<AUN PTJ PROJEK DONOR

111 PTEKIND 814013 114 PTEKIND 814013 22·1 -. Pl'EKIN[} 814013

~2 ~~J~.Q ~14On 223 PTEKIND 814013

- 224·- P-rEOND 814~--·-

226 PTEKIND 814013 227 PTEKIND 814013 228 PTEKIND 814013 229 PTEKIND 814013 335 PTEKIND 814013 441 PTEK1ND 814013

SENARAI JUMlAH-JUMLAH KECll :

110 EMOlUMEN

220 PERfHIDMA TAN DAN BEKALAI 330 ASET

440 PEMBERIAN DAN KENAAN BA't

Pl:RUNTIJkAN Pl:R8ElANJAAN TERKUMPUL PROJEK SEHINGGA THN lALU

125,200.00 63,810_90 0.00 0.00

6;0£IIHIO - 15-,-1-19: 1-1 _. 1,000.00 0.00

1,000.00 0.00 1,251100 ------- 6,916.62-

4,000:00 0.00 45,000.00 73,375.7-1

4,000.00 5,815.00 10,000.00 9;125.43 60,000.00 24,950.00

0.00 800.00

257,450.00 259,912.71

125,200.00 63,810.90

12,250.00 110,351.87

60,000.00 24,950.00

0.00 aoo.oo 251,450.00 259,9'12.77

Doi<lJmen In( a<iarall cetakan komputer c1an tfada tanc1atangan c1iperJukan

----_.- --_._---._----PERUNTIJKAN TANGUNGAN HAYARAN HELANJA HAKI

5EMASA 5EMASA 5EMASA 5EMASA PROJEK

61,389_10 0.00 0.00 0.00 61 ,339.10

0.00 0.00 644.44 644.44 -644.44 -69,'119+1- 0.00 0.00 0.00 -69;1'19.11

1,000.00 0.00 0.00 0.00 1,000_00 1,000_09 0.00 0.00 0.00 1,000.00

-5,666_62 0.00 0.00 0.00 -5,666.62 4,000.00 0.00 0.00 0.00 4,000 .00

-28;3-75:11 0.00 0.00 0.00 -28,375.71 -1,815.00 0.00 0.00 0.00 -1,815.£10

874.51 0.00 0.00 0.00 374.57

35,050.00 0.00 0.00 0.00 35,050.00

-800.00 0.00 0.00 0.00 -300.00

-2,462.71 0.00 644.44 644.44 -3;107.21

61,389.10 0.00 644.44 644.44- 60,744.66

-98,101.87 0.00 0.00 0.00 -98,101.87

35,050.00 0_00 0.00 0.00 35,050.00

-800.00 0.00 0.00 000 -800.00

-2,462.77 0.00 644.44 644.44 -3,1 07.21

~I 1l ~ ~: r J

• 1

No._

1.

2.

3.

Authors, Year, Title of paper, Name of journal or proceeding, Volume, Page Number

SETIANTO, W. B" NAWI, A. H. & MOHD. OMAR, A. 1<. (2008) Application of Chrastil

Model to The Virgin Coconut and Palm Kernel Oil Solub ility in Supercritica l Carbon

Dioxide. International conference on environmental research and technology. {pp.

921-925}, P. Pinang, Malaysia.

Setianto, W.B" Nik Norulaini, N.A., Abu Hanipah, N" Mohd Zu lhilmi, M . & Mohd

Omar, A. 1<' (2008). Solubi lity examination of virgin coconut oi l in supercritica l carbon

dioxide and its corre lation with existing model. In Proceedings of the 2nd

In ternational conference on science and technology (pp. 2187-2193), P. Pinang,

Malaysia.

NIK NORULAINI, N. A., SETIANTO, W. B" ZAIDUL, I. S. M. , NAWI, A. H" AZIZI, C. Y. M.

& OMAR, A. 1<. M. (2009) Effects of supercritica l carbon dioxide extraction

parameters on virgin coconut oil yield and medium-cha in triglyceride content. Food

Chemistry, 116, 193-19. (impact factor : 2.698)

International Conj'erence on Environmental Research and Technology (ICERT 2008)

Application of Chrastil Model to The Virgin Cocoout and Palm Kernel Oil Solubility in Supercritical Carbon Dioxide

WahyuB. Setianto*, Abu H. Nawi, Mohd. Omar Ab. Kadir

School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia *Corresponding author. Phone: +604 653 2110, Fax: +604 6585435

___~ __ . __ · ___ ~!pil-it~\fahyu~c.f.@yah.Q<2.~~m

ABSTRACT Supercritical carbon dioxide (SC-COz) extraction has been introduced as a clean technology for extraction process since it is exclusive of chemical utilization. Application of the SC-COz to vegetable oil extraction became an attractive technique due to its high solublbty, short extraciton hme, sImple punfiCafiOflanaa osence' of chemical residue in the oil. The application of SC-C02 to virgin coconut oil (VCO) and palm kernel oil (PKO) extraction has been performed. The equilibrium solubility ofVCO and PKO in supercritical carbon dioxide have been measured by means of extraction curve' analysis . The measurements were performed in the temperature range from 323 .1 5 K to 353. 15 K and pressures 20. 7 to 34.5 :MPa for VCO and 27.5 to 48.3 "NfPa for PKO. The solubility experimental data were correlated with Chrastil model, a density solvent base model. The experimental data were well fitted to the model by average absolute Jlercent deviation 2.20 and 3.84 for VCO and PKO respectively.

Keywords·: -Ghrastil-modeI-,-palIn-kerneLo.il, ... solubilit¥,_sup.ercritical _carbon dioxide, virgin coconut oiL

----------1. INTR,Op'UCTlo~-~·· ... · ~--. _

Supercritical .carbon dioxide (SC-C02) extraction is an attractive technology due to its relatively low critical temperature (31.1 0c) and critical pressure (7.38 :MPa) (McHugh and Krukonis, 1994). In the supercritical state, liquid-like density is approached, while viscosity is near that of normal gases, and diffusivity is about two order of magnitude higher than in typical liquid (Brunner, 1994). It makes the fluid become an excellent solvent. As the solvent is non-polar, the application for triglyceride extraction gives a pramising result. Using SC-COz salvent allaws extractian pracesses to aperate near ambient temperature. Furthermare, SC-COz is nan-taxic, can be used in food-grade fann for faad pracessing, and is cansidered to be an environmentally friendly solvent. It shauld be noted that we are using CO2 rather than dispasing it. Separation af extracts fram SC-COz is relatively simple, since the salute extract can be separated fram the SC-COz solvent by reducing the pressure af the flawing mixture thraugh an expansian valve.

In this study, the SC-C02 extraction technalogy was applied far the extract ian afvirgin cacanut oil (VCO). and palm kernel ail (PKO). In the extractian pracess, a single step extraction can be applied, in which the ails can be extracted directly fram the matrices without further purificatian ar separatian. A report af using af SC-COz extraction on caconut ail has been published (Celestino et aI. , 2006). The author suggested an ail cantent analysis of capra using SC-COz. It is reported that within less than ane our, 100% of caconut ail, as referred to. saxhlet extraction, cauld be extracted from the tissue using the pracess. However, further studies an the extractian, such as the ail solubility and mass transfer analysis have not been reported yet. The applicatian af SC-COz an PKO extraction has been reported in several publicatians (Hassan et aI. , 2000, Nik Namlaini et aI., 2004, Zaidul et ai. , 2007).The pracess has been described as a clean technalagy due to. the absent af chemical far sa lvent and refining far the pracess ..

Several vegetable (such as sunflawer, com, uCJ,mba and babassu) ail salubility in SC-COz have been carrelated ..Eith the madel (Soares et aL, 2007).J{awever, analysis afthe VCO and PKO solubility inSC-C0 2 using the sa lvent density base madel has nat been reported yet. The abjectives afthe study were to. examine the twa ail so lubility in SC-C0 2 and to. apply the Chrastil made I (Chrastil, 1982) an the solubility.

2. lVlATERlALS AND METHODS

2.1 Material The sa lubility af cacanut ail in supercritical CO2 was measured in this wark, whereas the palm kernel oil

so lubility data was acquired from previaus repart perfarmed by the same research group (Hassan et aI. , 2000).

Cleaner cech, concro t, treatment & remediacion cechnique 92 1

SOLUBILITY EXAMINATION OF VIRGIN COCONUT OIL IN SUPER CRITICAL CARBON DIOXIDE AND ITS CORRELATION

WITH EXISTING MODEL

Wahyu Bahari SetiantoU, Nik Norulaini Nik Ab.Rahmanb, Abu Hanipah Nawia

,

Mohd Zulhilmi Mokhtal'U, Mohd Omar Ab. Kadiru

"School at' Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Pulau Pi nang, Malaysia

"School of Distant Education, Universiti Sains Malaysia, 11 800 Minden, Pulau Pi nang. Malaysia

Emai l: wahyuscl@yuhoo.com

ABSTRACT. Coconut (Cocos nucijera L.) oil is a source of natural medium chain triglycerides (MCTs) with approximately 60% of Ihe oil cOn/en/ is ,."JCTs. The MCTs have been reported to have benefiCial eifeci on health Extraction of the oil has been performed using supercrilical carbon dioxide (SC-CO~. The extraclion technology has been introduced as a clean lechnology since it is exclusive of chemical utilization. Applicalion of Ihe SC-CO, to vegelable 011 extraction became an allraClive technique due 10 ils high soll/bilily. shOl'l extraction lime. simple purification and absence of chemical residue in the oil. In the present work. solubility of virgin coconut oil (VCO) in SC-CO, was examined. The Solubility examination was performed with dynamic method using a SC-CO, labora/ory scale extractor and phase behaVIOr examination using a view high-pressure vessel. The measZlremen/s were pe/formed al temperatures Fom 313.15 10 353./5 K and pressures Fom 20.7 10 34.5 MPa. The solZlbilily experimental data obtained/i'om dynamIC me/hod examination was correlaled with Chrastil and del Valle-AgUIlera model which are based on the CO} denSity. while the data Fom phase behavior examination was correlated with Peng-Robmson equation of state (£OS). The experlmen/al data was well fitted /0 the models by average ab~olllle

percent devialion (AAP D) 0.95 ond 4.02for Ihe Chras/i/ and del Valle-Aguilera model respectively and 2.62/01' Ihe

Peng-Robinson EOS.

1. Introduction

Coconut (Cocos nucifera L.) oil that is extracted from fresh coconut flesh is known as virgin coconut oil (YCO). The extraction involves a process without employing thermal treatment or food preservatives. Coconut oil obtained from copra, dried coconut has no taste or fragrance due to the refining process, whereas YCO has a fragrance and taste of coconut. The absence of heating and chemical usage in the oil makes it tasty and healthy. The antioxidant activity of YCO is superior to that of regular coconut oil, which is extracted from copra and of groundnut oil [ I]. Separation of the oil from the water oi l emulsion also can be accomplished by breaking the emulsion and creating an oil-oil emulsion [2], in which pure coconut oil is needed to be added to the coconut milk to extract the oil from the emulsion, and then the oil has to be separated from the water and protein with decantation. The existing mentioned process requires 24 to 48h and gives an oil yield of about 40% oil available in the coconut.

The oil is a natural so urce of medium chain tryglycerides (MCTs) in terms of fatty acids constituents with approximately 60% of the total oil content which are regarded as C6 to C12 fatty acids constituents. The MCTs constituents have been reported to have beneficial for the human health. The MCTs constituents are mainly utilized as a nutritional supplement for patient suffering from mal absorption caused by intestinal resection and also as a component of infant feeding tormulation [3] . It is also reported that MCTs constituents have beneficial effect on weight control and glucose as well as lipid metabolism [4].

The technology of supercritical carbon dioxide (SC-C02) was proposed to enhance the existing production process of virgin coconut o.il. Supercriti cal fluids are substances at pressure and temperature above their critical value. [n the supel'cl'itical region of a fluid, the phase state resembles one of the dense gases with properties that are generally intermediate to those of a gas and liquid. In tbe supercritical state liquid like density--.is approaclLed, while viscosity is near that of normal gases, and diffusivi ty is about two order of magnitude higher than in typical liquid [5]. A specific feature of the supercritical state of a fluid is its dense and highly compressible nature. This means that properties can be changed greatly with small changes in temperature or pressure. The tremendous variation in characteristics due to various conditions is causing differences in effects on solutes within the state conditions [6). The techno logy of SC-C02 is an attractive technology applied in many research activities around the globe due to its relatively low critical temperature (31.1 0c) and critical pressure (7.38 MPa) [7]. Using SC-C02 solvent allows extraction processes to operate near ambient temperature.

2 187

Food Chemistry 116 (2009 ) 193-197

_Contents~ lists available at ScienGeDireGt

.: \

Food Chemist ry -----. ~.

j ourna I h·o m e·p.age.: www.els.evi.er .. co·m/ I.ocat.e/fooctche,m

Effects of supercritical carbon dioxide extraction parameters on virgin coconut oil yield and medium-chain triglyceride content

N.A. Nik Norulaini a .• , W.B. Setianto b, I.S.M. Zaidul c, A.H. Nawi b, C.Y.M. Azizi d, A.K. Mohd Omar b

'Scl1ool oj' Discance Education. Universiti Sains Malaysia. 11800 Minden. 1'. I'inang. Malaysia b Scl100l oj' Indusnial Technology. UniversiLi Sains Maiaysicl. 11800 Minden. P. Pinang. Malaysia 'DeparoJ1ent oJ Food Science. Faadey oj' Food Science anci Tecl1nology. Universiti Put/'a Malaysia. 43400 UPM. Serdang. Selangor DE. Malaysia dCl1emical Engineering DeparoJ1ent. Universiti Teknologi Malaysia. 813 10 Skudai.jollOr. Malaysia

ARTICLE [NfO ABSTRACT

Artide history: Received 9 Decem ber 2008 Received in revised form 7 January 2009 Accepted 12 February 2009

Keywords:

Virgin coconut oil

The extraction of coconut oil has been performed us ing supercritical carbon dioxide (5C-C02 ). The ext rac­tions were performed at pressure and temperature r<l nges of 20.7-34.5 MPa and 40-80 0( . respect ive ly. It was observed that almost all (mo re than 99%) of the total oil could be extracted. Response surface meth­odology (RSM ) was applied to eva lua te the effects of the parameters (pressure. temperature and CO2 con­sumpt ion) on the extraction yie ld and mediu m-chain trig lyce rides (MCTs ), in terms of the fa tty acid content in the ex tracted oil. A correlation was established with p-va lues fOT both responses sign ificant at the 95% confide nce level.

Medium chain lriglyceri des Supercritica l CO, Extraction Response s urface methodology

1. Introduction

Coconut (Cocos nll cilera L) oil is a na tura l source of med iu m­cha in t rig lyce rides (MCTs) with a pproximate ly 60% of the total oi l content being MCfs. The term MCT refers to t riglyceride which is com posed of a glycerol backbone and three satu rated fatty acid s with chain length of 6-12 carbons. MCTs have been repotted to be beneficia l to hum a n hea lth. MCTs a re ma inly utili sed as a nut ri­tional supplement for patients suffering from ma labsorp tion caused by in testi na l resect ion and a lso as a component of infa nt feedi ng form ulas (Nandi, Gangopadh yay, & Ghos h. 2005). rVlarten. Pfeuffer. and Schrezenmei r (2006) reported t hat MCTs have bene­ficial effects on weight co n trol and g lucose, as we ll as li pid metab­o lism. Compa red wit h other triglycer ides that main ly conta in sa turated long chain fatty acids . MCTs have a lower melting poin t. s ma ller molecular size, lower sol id ificat ion temperature and lower energy density. These ciistillct chemical properties affect the ways in which MCTs are absorbed and metabo lized. MCfs have a lso been reported as tumoUl' inh ibitors wben consumed in a_diet (Cohen & Thomson, [987). and. if t hey a re mixed with phytos te ro l and high-o leic canola oil. t hey can deCl~ease plasma lipid content in overweight men (Ru dkowska, Roynelle, Naki1as i, & Jones . 2(06).

Coco nu t oil that is ex tracted from fres h cocon ut fles h is known as virgin cocon ut oil (VCO). The extraction invol ves a

• Corresponding author. Tel./ fa x: +6046585435. F.- mail address: nor1.!i.1in@u~~m.my (N.A. Nik NOfulain i).

0308~81461$ ~ see fro nt matter '9 2009 Elsevier Ltd . /\ 11 righ ts reserved. doi : 1 0.1 01 6/j.lclOdchem. 2009.02.030

© 2009 Elsevier Ltd. All rights reserved.

process that does not use thermal t rea tment or food preserva­tives. Coconut o il obta ined from copra, dried coconu t, has no taste o r fragrance, due to the refin ing process. w hereas vco has the fragrance a nd taste of coconu t. The a bse nce of healing and chemical treatm ent in the oil makes it tasty and healthy. The antiox idant activity of VCO is superio r to t ha t of regular cocon ut oil, which is ext racted fro m copra, an d a lso of ground­nut oi l (Nevin & Rajamoilan. 2005). The existing process produc­tio n of VCO basically is conducted thro ugh o il sepa rat ion from coco nu t m il k (Sukartin & Sitangga ng, 2005). Coconut m ilk can be obtained by e ithe r press ing fres h coconu t fles h w ithout addi­tional water or grat ing the coconut flesh followed by extracting the water-o il emuls io n with wate r. The oil can be separated fro m the e m ulsi on by means of boili ng, fe rmenta tion. re fr ige ra­tion or mechan ica l centrifuge. Separation of the oil from the water-o il emul sion can a lso be acco mpl ished by break ing the emulsion and creating an oi l-o il emul sion . in which pure coco­nut o il must be added to the coco nut m ilk to extract the oil from the emulsion . and then the oil m usc--be sepaTated from the wa ter and protei n w ith decantatio n. The exis ti ng process re­qu ires 24-48 h and produces an oil yie ld of about 40% of t he oil ava ilab le in the coco nut.

Although extractio n of nat ural compounds us ing SC-C02 has been reported as a promising techn ique by many researchers it is re markable that very few reports on the extraction of coconu t oil fro m copra using SC-C02 have bee n publ ished. Ad d itiona lly . tllere is a lack of fu ndamenta l ins ights in to the SC-C02 extraction process