䀸릤§⟴䀸ꮠ산산§산ꮠ 산§릤§산
§릤䬬ꮠ갬§산䨸 §릤산 §§鮼ઈퟰ왌ὨὨ왌ퟰ§ 魤牨산ꮠ§산릤䬬䬬§§䬬䀸䨸ꮠ산산산䀸산 牨§
SYNTHESIS AND CHARACTERIZATION OF ACETONITRILE LIGATED Cu(II)-COMPLEX
AND ITS CATALYTIC APPLICATION FOR TRANSESTERIFICATION OF FRYING OIL
IN HETEROGENEOUS PHASE
Rycce Sylviana Pratikha, Syukri*, and Admi
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Andalas University, Kampus Unand Limau Manis Padang, 25163
Received October 5, 2012; Accepted December 17, 2012 §
ABSTRACT
§
Catalysts have played an important role in many industries because they allow the reaction occurs faster. The aim of this work were to synthesize and characterize a Cu(II)-acetonitrile complex immobilized on modified silica and to investigate its catalytic activity at optimal condition (catalyst concentration, stirring rate, and the duration of reaction) in transesterification of frying oil. Fourier Transform Infrared (FTIR) and Nano Laser-Particle Size Analyzer (NL-PSA) were used to characterized the catalyst obtained, metal loading and leaching of the copper content was measured by Atomic Absorption Spectroscopy (AAS) and the formation of product from transesterification reaction was analyzed by Gas Chromatography-Mass Spectroscopy (GC-MS). FTIR spectra reveal a successful synthesis of modified silica and the immobilized Cu(II)-acetonitrile complex on it. NL-PSA Analysis showed that the catalyst possesed smaller particle size than the parent silica. Analysis with AAS confirms the stable catalysts formed because metal loading and leaching value were of 6.19 and 0.16%, respectively. The optimum conditions were found to be 0.80% catalyst concentration, 300 rpm stirring rate and 10 h duration of reaction
§
Keywords§modified silica; immobilization; transesterification; methyl ester; Cu(II)-acetonitrile§
ABSTRAK
§
Katalis memainkan peranan penting dalam dunia industri karena memungkinkan reaksi berlansung lebih cepat. Pada penelitian ini telah dilakukan sintesis dan karakterisasi kompleks Cu(II)-acetonitril yang diamobilisasi pada silika modifikasi dan penentuan aktivitas katalitik dari katalis yang dihasilkan pada keadaaan optimum yaitu konsentrasi katalis, kecepatan pengadukan, dan lama pengadukan. FTIR dan Nano Laser-Particle Size Analyzer (NL-PSA) digunakan untuk mengkarakterisasi katalis yang dihasilkan; metal loading dan leaching kandungan tembaga diukur dengan AAS; dan pembentukan metil ester dari reaksi transesterifikasi dianalisis dengan GC-MS. Spektra FTIR menunjukan bahwa silika modifikasi dan katalis teramobilisasi sukses terbentuk. Analisis NL-PSA menunujukan bahwa ukuran partikel dari katalis lebih kecil dibandingkan silika induk dan silika modifikasi. Analisis dengan AAS memberikan informasi bahwa katalis yang terbentuk cukup stabil karena nilai metal loading dan leaching adalah of 6,19 dan 0,16%. Kondisi optimum dari reaksi transestrifikasi ditemukan pada konsentrasi katalis 0,80%, kecepatan pengadukan 300 rpm dan dengan lama pengadukan 10 jam.
§
Kata Kunci§modifikasi silika; amobilisasi; transesterifikasi; metil ester; Cu(II)-asetonitril§ §
INTRODUCTION
산산䀸䬬§ꮠ䬬§산§ꮠ牨산§䬬䨸䬬산릤§ꮠ§䬬䀸 릤䬬ꮠ䬬§ 릤䬬䬬§䘐 ꮠ §ꮠ䬬§䨸䬬릤§§산릤§ 릤§산릤§ §릤산ꮠ䬬§ 산䬬릤§§ꮠ§ 산䬬릤§ 릤릤§산릤§ 牨갬릤릤䨸䬬§산§ 릤릤갬릤릤䨸䬬§산산䀸䬬䬬§§牨산ꮠ䬬§ 牨갬릤릤䨸䬬§ 산산䀸䬬䬬§산릤§릤릤§ 산§ 산§ § 릤§ 릤릤갬릤릤䨸䬬§릤§ §릤 산릤§릤산ꮠꮠ䀸§산§䬬릤릤ꮠꮠ䀸§䨸§ 릤䀸§산릤§릤䀸§ ꮠ ꮠ䨸§§䬬릤산산릤§ 牨§䨸§ퟰઈ㮴§鯈§ 릤§ 릤§䬬ꮠ릤§ 릤릤갬릤릤䨸䬬§산산䀸䬬䬬§산릤§牨릤§릤䬬ꮠ산릤§ꮠ§ꮠ䨸䬬ꮠ산§ 릤䬬䬬§ 릤䬬릤§산산䀸䬬䬬§산릤§릤산䬬䀸§§䬬릤산산릤§산§
릤䀸릤§䨸§ 릤䀸§ 산릤§산䘐산䬬§䨸릤§§ 릤ꮠ§䘐릤§ 산산䀸ꮠ§산ꮠꮠꮠ릤䬬§Ὠ㮴§
䀸릤§⟴䀸ꮠ산산§산ꮠ 산§릤§산
EXPERIMENTAL SECTION §
Synthesis of catalyst
⟴ꮠꮠ산§갬릤§䘐산䬬§ ꮠ䬬䀸§ 릤산릤§산§§ § §ퟰ§ § 릤§
Optimalization of the immobilized Cu(II) catalyst on transesterification of frying oil
산산䀸ꮠ§ 산ꮠꮠ䀸§ § 산산䀸䬬䬬§ 산ꮠ릤§ ꮠ§
RESULT AND DISCUSSION§ §
䀸릤§⟴䀸ꮠ산산§산ꮠ 산§릤§산 §
Fig 1. §䬬릤산§산§산릤§䬬ꮠꮠ산§§牨ꮠ ꮠ릤§䬬ꮠꮠ산§ §산 䀸䨸䬬§릤§䬬䨸 산릤§산§§산산䀸䬬§산ꮠ릤§ §
§
Fig 2. ꮠ䬬ꮠ䨸ꮠ§산§산ꮠ릤§䬬ꮠ릤§ §산릤§䬬ꮠꮠ산§갬릤§
牨ꮠ ꮠ릤§䬬ꮠꮠ산§산§산산䀸䬬§산ꮠ릤§ §
갬䨸䬬§ 牨§산䬬릤§䘐산릤§ퟰὨ㮴§ 릤§䬬릤䬬§산§산§ ퟰ牐§牨ઈퟰ§䘐산䬬§산䬬䬬ꮠ갬릤§ §䬬ꮠ 산릤§갬䨸䬬§⟴ꮠઈ鯈ઈ⟴ꮠ§ 苨ꮠꮠ산§산䬬§산릤산§산§牐§牨ઈퟰ§산§Ὠ牐§牨ઈퟰ§䨸릤§§ 릤ꮠ§릤 牨산ꮠ§ §⟴ꮠઈ鯈§ꮠ갬§ 牨§⟴ꮠ鯈§
산§ § 牨ꮠ ꮠ릤§䬬ꮠꮠ산§산릤산릤§䘐ꮠ §䘐릤산§ ꮠ릤䬬ꮠ䀸§산§牐§牨ઈퟰ§§ꮠꮠ산릤§ 릤§산릤산산릤§ §⟴ꮠઈ鯈§ 䘐ꮠ §牨릤산䬬§ꮠ갬§⟴ꮠઈ鯈ઈ苨§산§산§Ὠ§牨ઈퟰ§ 䘐산䬬§ 산䬬䬬ꮠ갬릤§§ઈઈ§䘐산갬갬ꮠ갬§ §산ꮠꮠꮠ䨸牨§산ꮠ§산䬬§ § 산산䀸䬬䬬§산ꮠ릤§산릤산§산§왌왌§牨ઈퟰ§ 䨸§ 릤§ 산䬬䬬ꮠ갬릤§§ꮠꮠ릤§≡§갬䨸§ꮠ산ꮠ䬬§ § 릤§갬산 릤§ 牨䨸䬬§ 릤§υ§ꮠ산ꮠ§ § 릤릤§왌§䘐䨸§
릤§릤 릤릤§산§뀨왌§산§牐왌§牨ઈퟰ§ퟰઈ㮴§§산산䀸䬬§ 䬬릤산§ꮠ䬬산릤산산릤§ §산䬬§산§Ὠ§牨ઈퟰ§ퟰퟰ§牨ઈퟰ§ 산§ퟰ牐§牨ઈퟰ§ 牨 §뀨왌
鮼§
ꮠ§䨸 릤牨릤§산䬬§ ꮠ릤䬬ꮠ䀸§산§Ὠ牐§牨ઈퟰ§ 牨§⟴ꮠઈ鯈§릤ꮠ갬§ꮠ§䬬䨸 §산산䀸䬬§
䘐릤산릤§ 산§ 릤§릤§ꮠ§산릤§䬬ꮠꮠ산§산䨸䬬릤§䀸§ ꮠ릤산ꮠ§릤䘐릤릤§䬬ꮠ산§갬䨸䬬§䘐ꮠ §䨸§牨릤산§ 릤릤§ 릤§산산ꮠ산ꮠꮠ䀸§ § 䬬 ꮠ 릤§§䬬릤 ꮠ갬§ ꮠ산ꮠ§산䬬§䨸§릤§산갬䨸릤§산䬬§산§䬬䨸릤䬬䬬 䨸§갬산 릤§ §䨸§산릤ꮠꮠ릤§牨릤 §§ 릤§牨ꮠ ꮠ릤§䬬ꮠꮠ산§ퟰ㮴§ §
NL-PSA Analysis§ §
ઈ⟴苨§ 갬산릤§ ꮠ 牨산ꮠ§ 산䨸§ 䬬ꮠ릤§ 산§ ꮠ䬬ꮠ䨸ꮠ§ §산ꮠ릤§§산§릤§䬬릤릤§ 牨§ꮠ갬§§산§ 산릤ꮠ갬§ §산릤§䬬ꮠꮠ산§ꮠ䬬ꮠ䨸ꮠ§ꮠ§ퟰ뀨ઈ§�牨§ 산갬릤§䘐ꮠ §牨ꮠ산릤§䀸§ퟰ§�牨§산ꮠ릤§䬬ꮠ릤§苨§ 산릤ꮠ갬§ꮠ䬬ꮠ䨸ꮠ§ § ꮠ䬬§牨산릤ꮠ산§ꮠꮠ산릤§ 산§ 릤§䬬ꮠꮠ산§䘐산䬬§산牨 䨸䬬§§
સꮠ ꮠ릤§䬬ꮠꮠ산§ 산䬬§산䘐§ꮠ䬬ꮠ䨸ꮠ§산§䬬牨산릤§ 산ꮠ릤§䬬ꮠ릤§ 산§ꮠ䬬§산릤§䬬ꮠꮠ산§䘐 ꮠ §䬬릤릤牨ꮠ갬䀸§산䬬§산§ 䬬릤ɬ䨸릤릤§ § 릤§ꮠ릤산ꮠ§릤䘐릤릤§苨왌§ 산䬬§
牨ꮠ ꮠ릤§䘐ꮠ §䬬ꮠꮠ산§䬬䨸 산릤§ 릤§갬산 릤§䨸§ 牨릤 §§牨ꮠ ꮠ릤§䬬ꮠꮠ산§ 릤§산ꮠ릤§䬬ꮠ릤§산§ ꮠ䬬ꮠ䨸ꮠ§䬬ꮠ갬 䀸§릤릤산䬬릤§ 산§산§릤§ 산산릤§ § ꮠ䬬§산산䀸ꮠ§산ꮠꮠ䀸§䨸릤§§산갬릤§䬬릤ꮠ ꮠ§䬬䨸 산릤§산릤산§ §
Atomic Absorption Spectroscopy (AAS)§ §
苨苨⟴§산산䀸䬬ꮠ䬬§ꮠ릤§ 릤§산牨䨸§ §牨릤산§ 산ꮠ갬§산§牨릤산§릤산 ꮠ갬§산릤§§䘐산䬬§ 䨸§ 산§ 릤§ 牨릤산§산ꮠ갬§ §䨸§ꮠ§ 릤§산산䀸䬬§䘐릤릤§ퟰ牐Ⳉ§䀸§ 牨산䬬䬬§산§䀸§䨸릤갬릤䬬§ퟰⳈ§䬬䬬§ꮠ§ 릤§䬬릤§ 산 릤§§ §릤산 ꮠ갬§릤䬬§ ꮠ䬬§䬬牨산§산䨸릤§ꮠꮠ산릤§ 산§ 릤§䨸§牨릤산§릤릤§䘐산䬬§䬬갬䀸§䨸릤§§ 릤§ 牨ꮠ ꮠ릤§䬬ꮠꮠ산§ 䨸갬 §릤릤䬬산ꮠ§ꮠ릤산ꮠ§
§
Catalytic Application at Optimal Conditions§ §
Catalyst concentrations
릤§ 䨸§ § 산산䀸䬬§ 릤산ꮠ§ 䘐산䬬§ 산산䀸릤§䀸§ઈસ⟴§§ꮠ갬§왌§䀸§산ꮠ갬§ퟰ뀨Ⳉ§ 산산䀸䬬§ꮠ§ 릤§牨ꮠ 䨸릤§ §牨릤 산§산§ 䀸ꮠ갬§ꮠ§ 릤§ 䀸ꮠ릤§ §牨릤 䀸§릤䬬릤§릤릤§ꮠ릤산䬬릤䬬§䨸ꮠ§산䨸§§ Ⳉ§䘐 ꮠ §산ꮠ§Ὠ牐Ⳉ§䨸§ 릤§䨸§ 산ꮠ릤§䘐릤릤§牨릤 䀸§릤䬬릤§䘐 ꮠ § 䨸§왌ퟰⳈ§牨릤 䀸§ 산牨ꮠ산릤§산§ퟰퟰ牐§牨ꮠ§릤릤ꮠ§ꮠ牨릤§산§왌牐Ⳉ§ 牨릤 䀸§릤산릤§산§ퟰ§牨ꮠ§릤릤ꮠ§ꮠ牨릤§苨§ ꮠ䬬§ ꮠ§ ꮠ갬 릤§ §䀸ꮠ릤§ §牨릤 䀸§릤䬬릤§䨸릤§§ 릤§牨䬬§ 䨸산릤§ 牨산ꮠ§ §牨릤 ꮠ릤§산ꮠ§䘐 ꮠ §ꮠ䬬§릤䀸§ ꮠ牨산§§ꮠꮠꮠ산릤§ 릤§산䬬릤䬬릤ꮠ ꮠ산ꮠ§ § 䀸ꮠ갬§ꮠ§ 산ꮠꮠ갬§ꮠ갬䀸릤ꮠ릤§산§ 산§ꮠ§䘐ꮠ§산䬬§릤§ 산䬬䬬䨸牨릤§산䬬§산§릤䀸§ 산§ퟰ왌㮴§릤산䬬릤§ §산산䀸䬬§ 릤산ꮠ§牨산릤§䀸ꮠ릤§ §牨릤 䀸§릤䬬릤§산ꮠ릤§ 산牨산ꮠ산䀸§䬬릤§䘐§§산牨䬬§릤§
§
Stirring rate
䀸릤§⟴䀸ꮠ산산§산ꮠ 산§릤§산 §
Fig 3. 산산䀸䬬§릤산ꮠ§䬬§산䀸§牨릤 䀸§릤䬬릤§
산ꮠ릤§ꮠ§ ꮠ䬬§䘐§
§
Fig 4. ⟴ꮠꮠ갬§릤ꮠ䀸§갬ꮠ릤䬬§䬬ꮠ갬ꮠ ꮠ산§ꮠ牨산§§
산산䀸ꮠ§산ꮠꮠ䀸§ § 릤§산산䀸䬬§䨸䬬릤§ꮠ§ ꮠ䬬§릤산ꮠ§
§
§
Fig 5. 䨸릤§ 牨릤 䀸§릤䬬릤§䨸§산§ 牨§릤산ꮠ§
ꮠ牨릤䬬§산ꮠ산ꮠ䬬§ §
산ꮠ릤§苨§왌§牨§䘐산䬬§ 䨸§뀨Ⳉ§ §䨸§ 산§ 산ꮠ§뀨ퟰⳈ§ §牨릤 䀸§ 산牨ꮠ산릤§ퟰ왌뀨Ⳉ§牨릤 䀸§ 릤산릤§산§왌Ⳉ§牨릤 䀸§䬬릤산산릤§산§ퟰퟰ§牨ꮠ§ 릤릤ꮠ§ꮠ牨릤§ ꮠ䬬§ 릤牨릤§산§릤§산갬䨸릤§ 산§산§ ꮠ䬬§산릤§ 릤§산䬬ꮠઈ릤䬬ꮠ§ §䬬䨸䬬산릤䬬§§ 산산䀸䬬§䬬䨸 산릤§릤산 릤䬬§ꮠ䬬§릤ɬ䨸ꮠꮠꮠ䨸牨§ 산§산䘐䬬§ 릤§ 산산䀸䬬§§䘐§ꮠ牨산䀸§
§
The duration of the reaction
苨䬬§산§릤§䬬릤릤§ꮠ§ꮠ갬§뀨§ 릤§갬릤§ §䨸산ꮠ§ §릤산ꮠ§䘐산䬬§䨸§ꮠ§ ꮠ갬 릤§䨸§산ꮠ릤§§ ꮠ䬬§ 산릤§ 릤§갬릤§ §䨸산ꮠ§ꮠ牨릤§ §릤산ꮠ§䘐릤릤§§牐§ 산§ퟰ§ §§䘐산䬬§ 䨸릤§牐牐§뀨§산§뀨ퟰⳈ§ § 䨸§ ꮠ䬬§ 산§䬬 䘐릤§산§䬬ꮠ갬ꮠ ꮠ산§릤 릤§ § 릤§ 䨸산ꮠ§ §산䬬릤䬬릤ꮠ ꮠ산ꮠ§릤산ꮠ§§산䘐§牨릤§ 䬬䨸䬬산릤§§ꮠ릤산§䘐ꮠ § 릤§䬬䨸 산릤§ §䬬䨸 §ꮠ牨牨ꮠꮠ릤§ 䨸§산산䀸䬬§
§
CONCLUSION §
牨牨ꮠꮠ산ꮠ§ § 䨸ઈ산릤ꮠꮠ릤§牨릤 § § 牨ꮠ ꮠ릤§䬬ꮠꮠ산§산§릤§릤 牨릤§산§牨ꮠ䬬ꮠ갬䀸§산§릤§ 산ꮠ릤§ꮠ§산䬬릤䬬릤ꮠ ꮠ산ꮠ§ § 䀸ꮠ갬§ꮠ§ 릤§산산䀸䬬§
䬬 䘐䬬§ꮠ䬬§ꮠ牨산§ ꮠꮠ䬬§산§ Ⳉ§산산䀸䬬§ 릤산ꮠ§산§왌§牨§䬬ꮠꮠ갬§산릤§䘐릤릤§ꮠ䬬§ 릤릤릤릤§§ 릤§䨸산ꮠ§ §릤산ꮠ§ꮠ牨릤§䬬ꮠ§§릤§ 䬬릤§ꮠ§ 릤§릤 §릤䬬릤산 §
§
ACKNOWLEDGEMENT§ §
릤§䘐䨸§ꮠ릤§ 산䬬§§સ산릤ꮠ산§ 릤牨ꮠ䬬䀸§ 산산䀸§䬬산 § § 릤ꮠ§ 릤§ꮠ§ 릤§§산§ઈ⟴苨§ 牨릤산䬬䨸릤牨릤§ 릤§䨸§ 산䬬§갬§§릤산§쀔산§ 산산䀸§산§苨﵌魤⟴§산산갬§산산䀸§ § 릤ꮠ§ 릤§ꮠ§苨苨⟴§산§ઈસ⟴§牨릤산䬬䨸릤牨릤§릤䬬릤ꮠ릤䀸§ §
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Ὠ§ ꮠ릤§સ§산§§산§સ산ɬ䨸산ꮠ릤§§ §J. Chem. Soc., Dalton Trans.§§ퟰퟰઈퟰퟰ § 릤䀸§§산§⟴산§§§J. Am. Chem.
Soc.§ퟰ왌§ퟰ§牐뀨牐뀨왌
牐§ 䬬ꮠ갬牨§苨§갬§﵌§산§ 릤ꮠ䬬§§왌§J. Catal.§ퟰ왌§ퟰ§ퟰ왌ퟰ
䀸릤§⟴䀸ꮠ산산§산ꮠ 산§릤§산
ퟰퟰ§산 牨산§§산§䨸릤ꮠ§﵌§牐§Iran. Polym. J.§ퟰ§왌§ퟰ牐ퟰ
ퟰ§⟴ ꮠ산산§⟴§산§ 산산§§뀨§J. Sci. Ind. Res.§§牐뀨왌
ퟰ왌§산䬬 ꮠ§쀔§산§苨䘐산§§§Energy Fuels§§ ퟰ왌ઈퟰ왌ퟰ§
ퟰ§산牨산ꮠ갬䬬ꮠ §苨§ꮠ䬬䨸산䀸산ꮠ§§산§산 ꮠ§§ §Indo. J. Chem§§왌§Ὠ§
ퟰ뀨§쀔산牨ꮠ§ ⟴§ 苨ꮠ산ꮠ§ § 산§ 䨸 산䬬牨산§ § ﵌ꮠ릤ꮠ산§ 릤산䬬ꮠ§ 산䬬릤䬬릤ꮠ ꮠ산䬬ꮠ§ 鯈§ 릤 산산§ 䨸§સ릤ꮠ§산牨ꮠ산§산산牨§릤산 䨸牨산§Proc.
Nat. Conf. Fundam. Appl. Technol.§ 䬬ꮠ䨸§ 릤갬ꮠ§⟴릤䨸䨸 §릤牨릤§ퟰ뀨§릤牨릤§Ὠ ퟰ§⟴䨸산§ § § 산릤§ ⟴릤䬬䀸:
Fundamentals and Applications§ § ꮠ릤䀸§ § ⟴䬬§§§§
ퟰὨ§산ꮠ산갬산§ ﵌§ ⟴䨸산§ § ꮠ䀸산ꮠ§ સ§ ꮠꮠ산§⟴§苨갬갬산ꮠꮠ§§苨ꮠ릤 §⟴§산§산牨산䨸§ §﵌산산릤ꮠ䬬ꮠ§﵌릤산䬬산牨산§﵌산산ꮠ䬬§릤산䬬ꮠ䬬§䬬ꮠꮠ산§ 䬬릤산牨§산ꮠ§䀸산갬§ꮠ릤릤 §릤갬산§릤ꮠ§䬬§갬릤§ Proc. Nat. Conf. Sci. Technol II, 산牨䨸갬§ 쀔ꮠ릤䬬ꮠ䀸§ퟰὨઈퟰ§릤牨릤§§
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