ISSN Vol. 25 No.1 April 2015

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. .1Jurnal

TApril 2012Vol22NoeknologiIndustri Pertanian

Jurnal

Teknologi Industri Pertanian

ISSN 0216-3160

Vol. 25 No.1 April 2015

TERAKREDITASI: SK Dirjen DIKTI No. 56/DIKTI/Kep/2012

Vol. 25 No. 1Jurnal Teknologi Industri PertanianApril 2015

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Volume 25, Nomor 1, 1-93 April 2015

PERUBAHAN KANDUNGAN KIMIA SARI ROSELA MERAH DAN UNGU (Hibiscus sabdariffa Linn.) HASIL PENGERINGAN MENGGUNAKAN CABINET DRYER DAN FLUIDIZED BED DRYER

Mardiah, Fransisca Rungkat Zakaria, Endang Prangdimurti, Rizal Damanik ... 1 ADSORPTION MODELING ON CARBON MONOLITHIC COLUMN FOR

METHYLENE BLUE REMOVAL

Darmadi, Medyan Riza, and Mirna Rahmah Lubis ... 8 PROSES HIDROLISIS ASAM DAN ENZIM PADA POLISAKARIDA

Euchema cottonii UNTUK BAHAN BAKU BIOETANOL

Pandit Hernowo, Dwi Setyaningsih, dan Bagus Sediadi Bandol Utomo ... 17 INVESTASI DAN PEMILIHAN TEKNOLOGI PENGGILINGAN PADA AGROINDUSTRI PADI DENGAN PENDEKATAN FUZZY STUDI KASUS DI KABUPATEN CIANJUR

Faqih Udin, Marimin, Sukardi, Agus Buono, Hariyadi Halid... 23 PEMANFAATAN KATALIS SILIKA ALUMINA DARI BAGASSE PADA

PEMBUATAN BIODIESEL DARI MINYAK GORENG SISA PAKAI

Sriatun , Taslimah, dan Linda Suyati ... 35 FORMULATING STRATEGIES TO IMPROVE FOOD SAFETY OF SMALL-MEDIUM ENTERPRISES BAKERIES THROUGH GOOD

MANUFACTURING PRACTICES

Yandra Arkeman,Triningsih Herlinawati, Dhani S. Wibawa, Himawan Adinegoro ... 43 PROSES REAKTIVASI TANAH PEMUCAT BEKAS SEBAGAI ADSORBEN UNTUK PEMURNIAN MINYAK SAWIT KASAR DAN BIODIESEL

Ani Suryani, Gustan Pari, dan Amelia Aswad ... 52 KARAKTERISASI PEPTON IKAN HASIL TANGKAP SAMPINGAN TIDAK LAYAK KONSUMSI SEBAGAI SUMBER NUTRIEN

PERTUMBUHAN MIKROORGANISME

Tati Nurhayati, Bustami Ibrahim, Pipih Suptijah, Ella Salamah, Risa Nurul Fitra, Eska Rizky Wiji Astuti ... 68 PERENGKAHAN KATALITIK METIL ESTER dari MINYAK LIMBAH CAIR

PABRIK MINYAK KELAPA SAWIT DENGAN KATALIS Cr/Mo/HZA DAN Ni/Mo/HZA

Agus Sundaryono, Dewi Handayani, Budiman, Sherly Winda ... 78 KARAKTERISTIK KOMPON KARET DENGAN BAHAN PENGISI ARANG AKTIF TEMPURUNG KELAPA DAN NANO SILIKA SEKAM PADI

Popy Marlina, Filli Pratama, Basuni Hamzah, Rindit Pambayun... 85

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Terakreditasi B berdasarkan Surat Keputusan Dirjen Dikti No 56/DIKTI/Kep/2012 tertanggal 24 Juli 2012 ISSN : 0216-3160

JURNAL TEKNOLOGI INDUSTRI PERTANIAN

Vol. 25, No. 1, 2015 Penanggung Jawab

Ketua Umum Asosiasi Agroindustri Indonesia dan Ketua Departemen Teknologi Industri Pertanian, FATETA - IPB

Ketua Dewan Editor Marimin (IPB) Dewan Editor

Agus H. Canny (AGRIN) Didik Purwadi (UGM) Dwiwahju Sasongko (ITB) Kadarsah Suryadi (ITB) M. Syamsul Ma’arif (IPB) Moh. Nasikin (UI) Moses L. Singgih (ITS) Tajuddin Bantacut (IPB) N. Taufiqurahman (LIPI) Editor Pelaksana

Ika Amalia Kartika (Ketua) Andes Ismayana

Dwi Setyaningsih Ono Suparno Titi Candra Sunarti Sekretariat Sri Martini Ketih Suketih Penerbit

Asosiasi Agroindustri Indonesia (AGRIN) dan Departemen Teknologi Industri Pertanian (TIN) Fakultas Teknologi Pertanian (FATETA) Institut Pertanian Bogor (IPB)

Alamat Redaksi

Departemen Teknologi Industri Pertanian Fakultas Teknologi Pertanian

Institut Pertanian Bogor

Kampus IPB Darmaga PO Box 220, Bogor 16002 Telp./Fax. (0251) 8621974, 8625088

e-mail: [email protected] ,

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Institusi Rp. 200.000,- belum termasuk ongkos kirim Permintaan langganan di kirim ke:

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No.Rekening 0275671500 atas nama Ketih Suketih

PRAKATA

Pembaca yang budiman,

Puji syukur kita panjatkan ke hadirat Allah SWT, atas berkat dan rahmatNya pada kesempatan ini kami dapat kembali menyajikan artikel-artikel menarik pada Jurnal Teknologi Industri Pertanian Volume 25 Nomor 1 Edisi April, Tahun 2015.

Semua artikel yang dimuat pada Jurnal Teknologi Industri Pertanian ini telah diseleksi dan ditelaah oleh Dewan Editor dan Mitra Bebestari yang kompeten. Hanya artikel-artikel berkualitas baik dan sangat baik yang dapat dimuat pada Jurnal Teknologi Industri Pertanian.

Topik-topik yang disajikan pada edisi ini mencakup: Perubahan kandungan kimia sari rosela merah dan ungu dengan alat pengering cabinet dryer dan fluidized bed dryer; Adsorption modeling on carbon monolithic column for methylene blue removal; Proses hidrolisis asam dan enzim pada polisakarida Euchema cottoni untuk bahan baku bioetanol; Investasi dan pemilihan teknologi penggilingan pada agroindustri padi dengan pendekatan fuzzy; Pemanfaatan katalis silika alumina dari bagasse pada pembuatan biodisel dari minyak goreng sisa pakai; Formulating strategies to improve food safety of small-medium enterprises bakeries through good manufacturing practice;

Proses reaktivasi tanah pemucat bekas sebagai adsorben untuk pemurnian minyak sawit kasar dan biodisel; Karakterisasi pepton ikan hasil tangkap sampingan tidak layak konsumsi sebagai sumber nutrien pertumbuhan mikroorganisme; Perengkahan katalitik metil ester dari minyak limbah cair pabrik minyak kelapa sawit dengan katalis Cr/Mo/HZA dan Ni/Mo/HZA. Sebagai penutup disajikan artikel yang berjudul Karakteristik kompon karet dengan bahan pengisi arang aktif tempurung kelapa dan nano silika sekam padi.

Kepada penulis dan mitra bebestari yang telah berkontribusi pada penerbitan jurnal edisi ini, kami menyampaikan terima kasih yang mendalam.

Kami mengundang rekan sejawat peneliti dan praktisi agroindustri mengirimkan naskah untuk disajikan pada jurnal ini. Saran dan kritik yang membangun dari pelanggan, pembaca dan para pihak lainnya sangat kami harapkan. Selamat membaca.

Ketua Dewan Editor

Marimin

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Jurnal Teknologi Industri Pertanian, April 2015 Vol. 25, No. 1 ISSN : 0216 - 3160

UCAPAN TERIMA KASIH

Dewan Editor menyampaikan terima kasih Kepada Bapak/Ibu/Sdr, atas kesediannya untuk menelaah naskah yang dimuat pada edisi ini.

Anggara Hayun Anujuprana, Pusat Pengkajian Kebijakan Peningkatan Daya Saing, Badan Pengkajian dan Penerapan Teknologi, Jakarta

Armansyah Halomoan Tambunan, Fakultas Teknologi Pertanian, Institut Pertanian Bogor Achmad Poernomo, Badan Penelitian dan Pengembangan Bioteknologi Kelautan dan Perikanan, Jakarta

Ary Achyar Alfa, Balai Penelitian Teknologi Karet, Bogor

Dyah Iswantini Pradono, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor Endang Widjajanti Laksono, Fakultas Matematika dan Ilmu Pengetahuan Alam, Universitas Negeri

Yogyakarta

Erliza Hambali, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Ekowati Chasanah, Balai Besar Riset Pengolahan Produk dan Bioteknologi Kelautan dan Perikanan, Jakarta Gayuh Rahayu, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor

Haznan Abimanyu, Lembaga Ilmu Pengetahuan Indonesia, Pusat Penelitian Kimia, Serpong Indah Yuliasih, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Isti Surjandari Prajitno, Fakultas Teknik, Universitas Indonesia, Depok Irzaman, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor

Joelianingsih, Fakultas Teknik, Institut Teknologi Indonesia, Tangerang Muslich, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Muhammad Dani Supardan, Fakultas Teknik, Universitas Syiah Kuala, Banda Aceh Mulyorini Rahayuningsih, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Nanik Purwanti, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Novizar Nazir, Fakultas Teknologi Pertanian, Universitas Andalas, Padang Sumatera Barat Nastiti Siswi Indrasti, Fakultas Teknologi Pertanian, Institut Pertanian Bogor Ridwan Rahmat, Balai Besar Penelitian dan pengembangan Pascapanen Pertanian, Bogor

Rokhani Hasbullah, Fakultas Teknologi Pertanian, Institut Pertanian Bogor Suprihatin, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Suherman, Fakultas Teknik , Universitas Diponegoro, Semarang Slamet Budijanto, Fakultas Teknologi Pertanian, Institut Pertanian Bogor Suryadi Ismadji, Fakultas Teknik, Universitas Katolik Widya Mandala, Surabaya

Sukardi, Fakultas Teknologi Pertanian, Institut Pertanian Bogor

Suryani, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor Udin Hasanuddin, Fakultas Pertanian, Universitas Lampung, Bandar Lampung Wagiman, Fakultas Teknologi Pertanian, Universitas Gadjah Mada, Yogyakarta

Zaenal Alim Mas’ud, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor

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Volume 25, Nomor 1, 1-93 April 2015

PERUBAHAN KANDUNGAN KIMIA SARI ROSELA MERAH DAN UNGU (Hibiscus sabdariffa Linn.) HASIL PENGERINGAN MENGGUNAKAN CABINET DRYER DAN FLUIDIZED BED DRYER

Mardiah, Fransisca Rungkat Zakaria, Endang Prangdimurti, Rizal Damanik ... 1 ADSORPTION MODELING ON CARBON MONOLITHIC COLUMN FOR

METHYLENE BLUE REMOVAL

Darmadi, Medyan Riza, and Mirna Rahmah Lubis ... 8 PROSES HIDROLISIS ASAM DAN ENZIM PADA POLISAKARIDA

Euchema cottonii UNTUK BAHAN BAKU BIOETANOL

Pandit Hernowo, Dwi Setyaningsih, dan Bagus Sediadi Bandol Utomo ... 17 INVESTASI DAN PEMILIHAN TEKNOLOGI PENGGILINGAN PADA AGROINDUSTRI PADI DENGAN PENDEKATAN FUZZY STUDI KASUS DI KABUPATEN CIANJUR

Faqih Udin, Marimin, Sukardi, Agus Buono, Hariyadi Halid... 23 PEMANFAATAN KATALIS SILIKA ALUMINA DARI BAGASSE PADA

PEMBUATAN BIODIESEL DARI MINYAK GORENG SISA PAKAI

Sriatun , Taslimah, dan Linda Suyati ... 35 FORMULATING STRATEGIES TO IMPROVE FOOD SAFETY OF SMALL-MEDIUM ENTERPRISES BAKERIES THROUGH GOOD

MANUFACTURING PRACTICES

Yandra Arkeman,Triningsih Herlinawati, Dhani S. Wibawa, Himawan Adinegoro ... 43 PROSES REAKTIVASI TANAH PEMUCAT BEKAS SEBAGAI ADSORBEN UNTUK PEMURNIAN MINYAK SAWIT KASAR DAN BIODIESEL

Ani Suryani, Gustan Pari, dan Amelia Aswad ... 52 KARAKTERISASI PEPTON IKAN HASIL TANGKAP SAMPINGAN TIDAK LAYAK KONSUMSI SEBAGAI SUMBER NUTRIEN

PERTUMBUHAN MIKROORGANISME

Tati Nurhayati, Bustami Ibrahim, Pipih Suptijah, Ella Salamah, Risa Nurul Fitra, Eska Rizky Wiji Astuti ... 68 PERENGKAHAN KATALITIK METIL ESTER dari MINYAK LIMBAH CAIR

PABRIK MINYAK KELAPA SAWIT DENGAN KATALIS Cr/Mo/HZA DAN Ni/Mo/HZA

Agus Sundaryono, Dewi Handayani, Budiman, Sherly Winda ... 78 KARAKTERISTIK KOMPON KARET DENGAN BAHAN PENGISI ARANG AKTIF TEMPURUNG KELAPA DAN NANO SILIKA SEKAM PADI

Popy Marlina, Filli Pratama, Basuni Hamzah, Rindit Pambayun... 85

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Adsorption Modeling on Carbon Monolithic Column………

8 J Tek Ind Pert. 25 (1): 8-16

ADSORPTION MODELING ON CARBON MONOLITHIC COLUMN FOR METHYLENE BLUE REMOVAL

PEMODELAN PENYERAPAN PADA KOLOM MONOLITIK BERLAPIS KARBON UNTUK PEMISAHAN METILEN BIRU

Darmadi*, Medyan Riza, and Mirna Rahmah Lubis

Department of Chemical Engineering, Faculty of Engineering, Syiah Kuala University Jl. Syech Abdurrauf No. 7, Banda Aceh, Indonesia, 23111

E-mail: [email protected]

Paper: Received 2 July 2014; Revised 6 October 2014; Accepted 11 November 2014 ABSTRAK

Model matematika telah dikembangkan untuk sistem batch dan kontinyu. Pada sistem batch, kinetika adsorpsi oleh monolith berlapis karbon dikaji untuk menganalisis kurva hasil penelitian dengan menggunakan model perkiraan Gaya dorong linear. Kinerja pada kolom monolith dievaluasi melalui kurva output. Model prediksi aliran sumbat yang terdispersi, dengan laju adsorpsinya dinyatakan oleh model tersebut, juga diidentifikasi. Kesetimbangan yang dinyatakan oleh isotermal Langmuir dan parameter laju yang termuat dalam dua persamaan, diperoleh dari penelitian secara batch. Kapasitas adsorpsi monolith karbon aktif tersebut adalah 190 mg/g dan koefisien gaya dorong liniarnya berkurang dari 0,011 menjadi 0,0052 per menit dengan kenaikan konsentrasi awal metilen biru dari 10 hingga 50 ppm. Prediksi yang menggunakan perkiraan gaya dorong linear untuk laju adsorpsi tersebut sesuai dengan data output penelitian.

Kata kunci: adsorpsi, kurva output, gaya dorong linear, kolom monolith, metilen biru

ABSTRACT

Mathematical models of adsorptionon carbon monolithiccolumn for methylene blue removalwere developed for batch and continuous systems. For batch system, kinetics of adsorption by carbon coated monolith was studied to analyze experimental uptake curves by using approximation model oflinear driving force.

Performance for monolith column was evaluated through breakthrough curves. A predictive model of dispersed plug flow, with the adsorption rate stated by the model, was also identified. Equilibrium represented by the Langmuir isotherm and rate parameters contained in two equations wasobtained from batch experiment. Capacity of activated-carbon-monolith adsorption was 190 mg/g and linear driving force coefficient decreased from 0.011 to 0.0052 min

^-1

with a rise of initial concentration of methylene blue from 10 toward 50 ppm, respectively.

Prediction using linear driving force approximation for adsorption rate fited in with experimental breakthrough data.

Keywords: adsorption; breakthrough curve; linear driving force; monolith column, methylene blue INTRODUCTION

Activated carbons in the form of powder or granule are commonly implemented in fixed-bed column. Fixed-bed columns have some disadvantages, such as maldistribution (resulting in non-uniform path of adsorbate to adsorbent surface, and non-optimally local conditions), large pressure drop in the bed, and sensitivity toward fouling by impurities. Activated carbon particle should be small in general relating to adsorptive activity. However, smaller particle will result in greater pressure drop (Cybulski and Moulijn, 2006). These disadvantages can be overcome by monolithic structure, which can be considered as a bundle of capillaries having a honeycomb-like shape.

Activated carbon monoliths have been proposed as adsorbent of pollutants from gas stream (Yates et al., 2000; Yates et al., 2003; Gadkaree, 1998). As compared to gas adsorption, liquid

adsorption using activated carbon monolith has received so little attention. Adsorption of methylene blue (MB) using activated-carbon-coated monolith to determine its capacity from aqueous solution has been performed (Darmadi et al., 2008).

In this study, the performance for liquid adsorption on the activated carbon coated monolith was investigated by using MB as a model dye. A mathematical model describing adsorption rate on the monolithic column was developed to predict breakthrough curves. Linear driving force (LDF) approximation were used in a batch system.

Therefore, no adjustable parameters were required in the model.

MATERIALS AND METHODS

Materials

The materials used in this research were ceramic monoliths (25 mm diameter and 100 mm

Jurnal Teknologi Industri Pertanian

25 (1):8-16 (2015)

*Correspondence Author

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Darmadi, Medyan Riza, and Mirna Rahmah Lubis

J Tek Ind Pert. 25 (1): 8-16 9

length) that were supplied by Beihai Huihuang Chemical Packing Co. Ltd., GuangXi, China. The chemical compositions of the monolithic substrate, as reported by Beihai Huihuang Chemical Packing Co. Ltd., are MgO 13.9 ± 0.5%, SiO

₂

50.9 ± 1%, Al

₂

O

₃

35.2 ± 1%, and others < 1%. Monolithic channels‟ cell shape was square with width of 1.02 ± 0.02 mm, wall thickness of 0.25 ± 0.02 mm, and channel density of 400 cpsi. Monolithic structure of 400 cell per square inch was coated by carbon.

Chemicals used in the carbon-coated monoliths were furfuryl alcohol 99% (FA) (Acros Organics, Geel, Belgium), pyrrole 99% (Acros Organics, Geel, Belgium), nitric acid 65% (Acros Organics, Geel, Belgium), and poly ethylene glycol (PEG) with 1500 g/mol molecular weight, further called PEG-1500 (Acros Organics, Geel, Belgium). For adsorption application, standard dye (methylene blue) was used.

Powder of the methylene blue was supplied by BDH Gurr-Cersistain, England, then directly utilized without further treatment.

Surface and Pore Volume Analysis

The pore structure (pore volume distribution and Brunauer-Emmett-Teller (BET) surface area) of carbon monolith was measured by nitrogen adsorption at 77 K. The pore volume was calculated by the Barret-Joyner-Halenda (BJH) method.

The specific surface area of porous carbons was usually measured by gas adsorption measurements using the BET theory (Gregg and Singh, 1982). Nitrogen adsorption at 77 K was widely used, although argon at 77 K was also used.

For carbon with surface areas less than 5 m

²

g

^-1

, krypton at 77 K might be preferably as adsorptive gas because of its low-saturation-vapor pressure (McEnaney and Mays, 1989). Lozano-Castello et al.

(2004) stated that molecule of nitrogen at 77 K cannot reach the narrowest microporous carbon because of diffusional limitations. Adsorption by using carbon dioxide at 273 K was recommended to obtain complete characterization of the narrowest micropores.

BET developed the first theory to successfully describe multilayer adsorption of gases on a wide range of porous and non porous solids (Do, 1998). For the reason, BET equation was accepted as standard equation in adsorption analysis to obtain specific surface areas of solids. It stated that the first adsorptive layer was localized on surface sites with uniform energy, and subsequent layers were analogous to adsorbate condensation (Gregg and Singh, 1982). Linear form of the BET equation is:

( )

where n is mole adsorbed at pressure p to saturated vapor pressure p

^o

, n

_m

is the mole of adsorbate required to cover surface monolayer, and c is dimensionless constant given by

(

) ( )

where q

₁

- q

₂

is heat of adsorption, q

₁

is heat of adsorption in the first adsorbed layer, q

₂

is heat of adsorption in subsequent layers, R

_g

is ideal gas constant, and T is temperature.

Polymerization

Polymerization reaction performed in reactor referred to method proposed by Vergunst et al. (2002). Monoliths were immersed in polymer solution for 15 minutes. The duration was made shorter compared to previous research which is 24 hours (Mohamad et al., 2014) in order to save immersing time. Optimization by Box-Behnken design was performed to investigate interaction and effects of concentration and molecular weight of PEG, as well as carbonization temperature on pore volume of carbon coated monolith (Darmadi et al., 2009). Characterization of carbon by using thermal- gravimetric analysis, elemental analysis, textural analysis, and scanning electron microscopy had been carried out by Darmadi et al. (2009). Amount of carbon coated on monolith after carbonization was about 15.42 wt% of bare monolith.

Kinetic Measurement

Kinetic experiment was conducted in a finite adsorber unit. It is an agitated batch adsorber with a 1.00 L cylindrical glass vessel containing 500 mL liquid. Mixing was provided by a monolithic impeller. The agitator was driven by an Overhead Stirrer Kika Labortechnik Type Rw 20. Study of batch contact time resulted in data of kinetic in curve type of time versus reduced concentration. Carbon- coated monolith of 1.6 g in each experiment was brought into contact with adsorbate solution of 500 mL at different initial adsorbate concentrations of 10, 20, and 50 mg L

^-1

. In regular time intervals, samples of approximately 2 ml were obtained by sampling system, then placed in sample bottles.

Withdrawal of the sample was started at t = 0 to 600 minutes every 10 minutes for the first half hour, every 30 minutes for the next an hour and a half, every 1 hour for the rest, then run was terminated.

Each of the samples was tested to determine solute concentrations by utilizing UV-vis spectrophotometer at wavelength of 664 nm.

Column Adsorption Studies

Column studies were performed to

investigate continuous flow of adsorbate through

monolithic column. Adsorption unit was an acrylite

column with length of 40 cm and inner diameter of

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10 J Tek Ind Pert. 25 (1): 8-16

26 mm. Column was made in particular structure in order to withdraw its samples in different heights (25, 30, and 35 cm) to evaluate breakthrough curve at various bed heights. During research, the column was continuously fed by a 20 mg/L methylene blue solution using peristaltic pump (Ismatec, Ecoline VC-280, Germany). The flow rates were adjusted by setting peristaltic pump switch on rates of 1, 2, and 3, respectively. Up-flow condition was selected to facilitate the accuracy in controlling flow rate of the adsorbate.

Column had been run in three types of flow rate in the range of 1.725 - 4.645 mL/min. The effect of adsorbate concentrations was also investigated by employing 10, 20, and 50 mg/L feed adsorbate concentrations. Samples (~5 mL) were withdrawn in certain interval of time starting from t = 0 to 600 minutes (10 hours). Each sample was tested to determine solute concentrations by utilizing UV-vis spectrophotometer at a wavelength with the maximum absorbance of 664 nm.

Modeling of Adsorption Process

Complete explanation of the mass transfer in adsorbents required solution of partial differential equations (PDEs). The explanation was written by changing equation of diffusion for adsorbent into space-independent approximation in determining rate of adsorption, which was LDF approximation.

First, LDF model (Chuang et al., 2005) for batch system was derived with some assumptions:

adsorbate concentration throughout bulk of solution in tank is homogeneous; at initial time (t = 0), solute concentration is uniform throughout the solution; the adsorbate concentration in its adsorbent at initial time is zero; volume of reactor is constant; the adsorption rate of adsorbate by adsorbent is linearly proportional to driving force, stated as a difference between concentration of surface and average concentration of adsorbed-phase; and system is isothermal. Mass conservation equation in batch condition is stated as:

is the concentration in liquid phase (mg/L), is liquid volume (L), M is the mass of adsorbent (g), and is average concentration of adsorbed phase per unit mass of adsorbent (mg/g). In solid phase, the average concentration is given by LDF approximation (Gleuckauf, 1955):

where q

^*

is concentration of the adsorbed phase at particle surface in equilibrium with bulk

concentration (mg/g), and , LDF kinetic constant (1/s), is given by (Zabka et al., 2006):

where D

_eff

is pore diffusion (m

²

/s), R

₁

is monolith radius (m), R

₂

is radius of the monolith channel wall (m).

For square channel, Patton et al. (2004) gives:

and

where is diameter of the monolithic channel (m) and is the thickness of carbon coated (m).

Performance of a monolithic column is analyzed by studying its breakthrough which is outlet responses of a monolith bed toward inputs. In order to derive mathematical model of carbon monolithic column, the following assumptions are used: uniform flow distribution in the monolithic column; unvaried parameters of mass transfer and physico-chemical properties throughout monolithic column; each channel is identical; carbon is initially free of adsorbate; isothermal operation; radial diffusion is ignored; and mass transfer within the adsorbent is described by LDF model. Using above assumptions, material balance in bulk phase of a monolithic channel gives:

where is concentration of bulk liquid phase (kg/m

³

), is axial coordinate (m), is time (s), is interstitial velocity of fluid in monolithic channel (m/s), is monolithic structure porosity, and is axial dispersion coefficient (m

²

/s).

The boundary and initial conditions are

dt

q M d dt V dC 



C V

q

) ( q

^*

q dt k

q d

LDF





k

LDF

2 2 2 2 1

2 1

) (

8 R R

R

k

_LDF

D

^eff

 

 R 2 a

1



2 1

2

4 ( )

R a t t

R 

^w _w

 

 a t

w

t q z

D C z v C t C

m m ax

z



 



 



 

 





 ) 1 (

2 2

C

z t

v

z



m

D

ax

0 ) , 0 ( ,

0 ) , 0

( t  z  and q t  z  C

C

F

z t

C ( ,  0 ) 

………..….. (3)

…………..….. (4)

……….….. (5)

………....….. (6)

…………...….. (7)

...….. (8)

... (9)

... (10)

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J Tek Ind Pert. 25 (1): 8-16 11

where C

_F

is initial concentration (kg/m

³

). Dispersion coefficient, , can be represented by (Douglas, 1984):

where and are geometrical constants. For monolithic channel, (Zabka et al., 2006) gives = 0.85 and = 3.68, respectively. The governing Equation (8) and Equation (12) are developed by combining effects of adsorption equilibrium, mass transfer, and dispersion. Information concerning adsorption equilibrium for adsorbate-adsorbent system is provided by measurements made in batch studies. The LDF mass transfer coefficients ( ) are obtained from matching a batch model with experimental uptake rate data. Column model is then used to predict breakthrough curves in a monolithic column. Note that the model does not have any adjustable parameter.

Numerical Simulation

The column model described previously is non-linear PDE. The PDE was discretized in spatial domain with orthogonal collocation (OC) method (Villadsen and Michelsen, 1978; Richard and Duong, 2012; and Choong et al., 2006). This set of ordinary differential equations (ODEs) was solved by using MATLAB subroutine ODE15s. It was found that twenty (20) interior collocation points give balance between computational speed and accuracy. In assuring appropriateness of the OC method, discrete scheme was verified by heat conduction in finite slab and plug flow-adsorption- model cases, and analytical solutions. Conformity for both cases was excellent.

In order to solve Equation (3), equilibrium adsorption capacity and initial conditions have to be known. The governing Equation (3) and Equation (4) from a set of ODEs, are solved simultaneously to

obtain concentration of fluid phase as a function of time. The linear driving force mass transfer coefficient ( ) is determined by matching simulation with experimental data.

RESULTS AND DISCUSSION

Specific surface area and pore volume for the carbon monolith are indicated in Table 1. These results confirm that the carbon monolith has relatively low specific surface. The equilibrium relationship between the activated carbon monolith and dye are described well by using the Langmuir isotherm:

( ) where C

^*

is concentration in the bulk fluid phase (mg/L).

The linear driving force mass transfer coefficients ( ) are extracted by solving Eq. 3 for batch system in both average concentration in solid phase and initial concentration. Then solution obtained is matched with kinetic data (Fig. 1). The best fit values are then listed (Table 2). Based on correlation coefficients, R

²

for monolith, the monolith can be considered as better adsorbent that carbon coated monoliths 8000 whose R

²

is 0.978 (Yi et al., 2013).

It is evident that k

_LDF

and D

_eff

depends on initial concentration. Both k

_LDF

and D

_eff

decrease with an increase of dye concentration. It indicates that there is an increase of affinity energy with progressive filling of site. Therefore, dye is strongly bonded to adsorbent surface, which reduces its diffusion rate from site to site ( Abd et al., 2010).

Adsorption capacity obtained is 190 mg/g (relatively larger than capacity of methylene orange, i. e. 28 – 132.7 mg/g (Willie et al., 2013), and much higher compared to that of

-carotene, i. e. 62.118 mg/g

(Muhammad et al., 2011).

Table 1. Specific surface area and pore volume for carbon monolith tested in nitrogen adsorption at temperature of 77 K

Sample S

_BET

(m

²

/g

) Activated

Carbon 431.0000 0.3800 186.5500 0.2313

Table 2. Parameters of LDF model for adsorption of MB at various initial concentrations Initial Conc. (ppm)

k_LDF

(min

^-1

)

D_eff

×10

⁸

(cm

²

s

^-1

)

R²

10 0.01100 6.932 0.9865

20 0.00825 6.661 0.9974

50 0.00520 4.199 0.9945

0 ) ,

( t z  L  dz

dC

D

ax

z eff

ax

D a v

D  

₁

= 0.00520 min

^-1

.

Breakthrough curve in each experiment is resulted from the experiment concentration versus time data. Figure 2 depicts breakthrough curves for MB removal with carbon coated monolith at three different dye feed concentrations, 30 cm height of bed, and 1.725 mL/min rate of flow. Shape difference observed at the breakthrough curve is ascribed to varied adsorption-driving-force because this system has the same flow rate, i.e. the same hydraulic loading. Breakthrough curves are flatter in low concentrations, which indicates mass transfer zone that is relatively wider, and film-controlled process. Conversely, an increase of initial adsorbate concentration increases slope of the breakthrough curve that reduces time needed before generation of carbon. It indicates that concentration change at the beginning could modify rate of adsorption and breakthrough time, hence difussion process depends on concentration (Foo and Hameed, 2012).

At constant flow rate, an increase of dye concentration reduces throughput until breakthrough.

This is because high adsorbate concentration makes carbon saturated more quickly, so that decreases breakthrough time. It can be concluded that higher dye concentrations reduce the treating times because carbon coated monolith is saturated more quickly (Walker and Weatherley, 1997). The results indicates that the modeling is favorable because there is relationship between concentration at the beginning with brakthrough time, not as for phenol adsorption (Anisuzzaman et al., 2014).

Breakthrough curve at different bed heights are indicated as plot of the dimensionless concentration versus time (Figure 3). It indicates that adsorber capacity increases at higher bed-depths or carbon mass. It also confirms that volume of solution treated and adsorbate removal increases as bed depth increases (Hasfalina et al., 2012). This

behavior is favorable since higher carbon mass means that there are more available adsorption sites for MB. However, breakthrough curves indicated in Figure 3 do not look like typical profile of “S-shape”

that is resulted in ideal adsorption system. Similar patterns of breakthrough curves are obtained for adsorption of reactive dyes, tectilon red 2B, tectilon blue 4R-01, as well as tectilon orange 3G with adsorber of Filtrasorb 400, and for adsorption of acid dye using granular activated carbon (Walker and Weatherley, 2000; Al-Degs et al., 2007).

Deformed breakthrough curves are attained because of two reasons: (1) adsorption kinetics of MB are slow on carbon coated monolith that is porous, where slow MB kinetics makes breakthrough faster, consequently results in “S”

breakthrough shape that is incomplete, and (2) utilization of small scale-column-apparatus commonly results in adsorption breakthrough curve (Al-Degs et al., 2007; Crittenden et al., 2005). Zone of adsorption along bed decreases throughout the bed height at particular rate which suggests that higher bed height is probably necessary for dye adsorption.

The tendency takes place at adsorption of dye material as a result of its large molecular structure so that its resistance toward internal diffusion is extremely higher compared to that of smaller molecular structures such as phenol.

Breakthrough curves for three types of flow rate, 30 cm fixed bed height, and 20 ppm initial concentration are indicated in Figure 4.

Breakthrough curve shape indicates internal

resistance in column, as well as relative effect in

mass transfer parameter for all conditions of

operation. Apparently, breakthrough point occurs

earlier at higher flow rates, implying shorter column

life.

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J Tek Ind Pert. 25 (1): 8-16 13

Figure 2. Breakthrough curve for different feed dye concentrations, 30 cm height of bed, and 1.725 mL/min rate of flow

Figure 3. Breakthrough curves of MB adsorption on various bed heights at 1.725 mL min

^-1

flow rate, 2.5 pH, and C

₀

of 20 ppm

Figure 4. Breakthrough curves of MB adsorption on various flow rates, 20 ppm feed concentration, bed height of 30 cm, and pH of 2.5.

0 2 4 6 8 10

0 60 120 180 240 300 360 420 480 540

C/Co (×10-1)

Time (min)

Exp Co = 10 ppm Exp Co = 20 ppm Exp Co = 50 ppm Simulation

0 2 4 6 8 10

0 60 120 180 240 300 360 420 480 540

C/Co (×10-1)

Time (min)

Exp. Bed Height 25 cm Exp. Bed Height 30 cm Exp. Bed Height 35 cm Simulation

0 2 4 6 8 10

0 60 120 180 240 300 360 420 480 540

C/Co (×10-1)

Time (min)

Exp. Fz = 1.725 mL/min Exp. Fz = 2.840 mL/min

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14 J Tek Ind Pert. 25 (1): 8-16

Breakthrough curves are also premature in larger flow rates, indicating that rate of adsorption is controlled by internal diffusion, and a narrow mass transfer zone occurs (Ahmad et al., 2007). It is also because of decrease in contact time between adsorbent and dye at higher flow rate (Walker and Wetherley, 1997). Besides, it is attributable to insufficient contact time of adsorbate in column to enable adsorbate diffuse into monolith pores (Salman et al., 2011). Therefore, solution weakly spreads or diffuses into monolith particle that causes time quicker to achieve saturation, or lower efficiency (Mohammad et al., 2012).

Breakthrough curves are flatter for lower rates indicating that effect of film resistance is more prominent, service time of the bed is longer, and zone of mass transfer is larger. It is reasonable because boundary layer around particles is thicker in lower flow rate that it increases external mass transfer resistance. It also indicates that adsorption is incomplete and leads to steep breakthrough result in initial operation (Ai and Ahmad, 2014). Effects of process parameters on breakthrough curve are also investigated. Breakthrough curves for all parameters are not like characteristic of „S‟ shape profile resulted in ideal adsorption system; it is connected to adsorbate molecular size. Most research performed on adsorption of dyes indicates similar profile of breakthrough curves to profile reported here. It appears that simulations performed by predictive model fits very well to the experimental breakthrough curve (Figures 2 - 4).

CONCLUSIONS AND RECOMMENDATION

Conclusions

LDF model for monolithic system was developed to extract LDF mass transfer coefficients ( ) by fitting the simulation to experimental data of uptake rate. Comparison of results by the LDF model and experiment was good with of 1.10 × 10

^-2

, 8.25 × 10

^-3

, and 5.20 × 10

^-3

min

^-1

at concentrations of 10, 20, and 50 mgL

^-1

, respectively.

A predictive model of dispersed plug flow, with adsorption rate stated by the LDF model, was developed to estimate breakthrough curve of monolith column. Parameters of the model were determined by batch adsorption experiments.

Simulation result obtained fits well to the experiment. Optimization could carried out with respect to geometric properties of the monolithic cell density and thickness of carbon coating layer. The LDF model employed in this work had its limitations as it assumes space independent approximation for the rate of adsorption. It is interesting to consider some of new rate models for adsorption. Activated carbon monolith was usable in other processes, i.e.

recovery of beta-carotene from palm oil, multi- component dye adsorption, and catalyst support in

hydrogenation reaction. Investigation of desorption and regeneration of activated carbon monolith is required.

Recommendation

Optimization can be carried out with respect to geometric properties of the monolithic cell density and thickness of carbon coating layer. The LDF model applied in this research should be replaced with new models e.g. film-pore- concentration-dependent-surface-diffusion model.

Activated carbon monolith is usable in recovery of beta-carotene from palm oil, multi-component dye adsorption, and catalyst support in extremely exothermic reaction. Furthermore, investigation of desorption and regeneration of activated carbon monolith is also required in the future.

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Gambar 1. Hubungan antara konsentrasi natrium perkarbonat, jumlah air dan daya serap air setelah perendaman selama 2 jam

Gambar 2. Interaksi antara konsentrasi natrium perkarbonat dan jumlah air terhadap kadar minyak

Tabel 1. Komposisi media transmisi Komposisi Jumlah (g/L)

KH

₂

PO

₄

3 MgSO

Kesimpulan ditulis secara ringkas tetapi menggambarkan substansi hasil penelitian yang diperoleh.

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Jurnal ini direferensikan sebagai J Tek Ind Pert., untuk jurnal-jurnal lainnya gunakan singkatan-singkatan berdasarkanChemical Abstracts abbreviations.

Jurnal

Sunarti TC, Nunome T, Yoshio N, Hisamatsu M.

2001. Study on outer chains from amylopectin between immobilized and free debranching enzymes. J Appl Glycosc.48 (1): 1-10.

Buku

Baker RW. 2004. Membrane Technology and Application. 2

^nd

ed. West Sussex: John Wiley

& Sons, Ltd.

Chapter dalam Buku

White PJ dan Tziotis A. 2004. New corn starch. Di dalam Eliasson AC (ed.),Starch in Food:

Structure, function and application.

Cambridge: CRC Press. P295-320.

Prosiding

Sunarti TC dan Yuliasih I.2006. Fractionation of Sago Starch Using Hot Water Solubiliza-tion Method.Proceedings of Malaysian Chemistry Conference 2006–International Conference on Green Chemistry. Petaling Jaya, Malaysia.19- 21 September 2006.

Tesis/Disertasi

Yuliasih I. 2007. Fraksinasi dan asetilasi pati sagu serta aplikasinya sebagai campuran plastik sintetik. [Disertasi]. Bogor: Institut Pertanian Bogor.

0 2 4 6 8 10 12

70 50 30

Jumlah Air (%)

Kadar Minyak (%)

Natrium perkarbonat 2%

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Jurnal Elektronik

Romo DMR, Grosso MV, Solano NCM, Castano DM. 2007. A most effective method for selecting a broad range of short and medium chain-length polyhidroxyalcanoate

producing micro-organisms. Electron J Biotechnol. 10:e349-57, doi 10.2225.

Paten

Robinson JM. 2010. Methods of digesting cellulose to

glucose using slats and microwave (muwave)

energy. US Patent No: US2010/0044210 A1.

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. .1Jurnal

TApril 2012Vol22NoeknologiIndustri Pertanian

Jurnal

Teknologi Industri Pertanian

ISSN 0216-3160

Vol. 25 No.1 April 2015

TERAKREDITASI: SK Dirjen DIKTI No. 56/DIKTI/Kep/2012

Vol. 25 No. 1Jurnal Teknologi Industri PertanianApril 2015