⟴ꮠ﵌산산䘐산ꮠ릤산
릤䬬ꮠ갬산䨸 릤산 鮼ઈઈ뀨왌뀨 魤牨산ꮠ산릤䬬䬬䬬ꮠ산산䘐산ꮠ䀸산 ꮠ
KINETICS AND MECHANISM OF Ni/ZEOLITE-CATALYZED HYDROCRACKING
OF PALM OIL INTO BIO-FUEL
Sri Kadarwati1,*, Fitri Rahmawati2, Puji Eka Rahayu1, Sri Wahyuni1, and Kasmadi Imam Supardi1
1
Department of Chemistry, Semarang State University Bld. D6 level 2, Kampus Sekaran, Gunungpati, Semarang 50229 2
PT. Wahana Citra Nabati, Jl. Rawa Sumur I Blok EE/5 Kawasan Industri Pulogadung
Jakarta Timur, 13930
Received January 2, 2013; Accepted March 22, 2013
ABSTRACT
Kinetics and mechanisms of Ni/zeolite-catalyzed cracking reaction of methyl ester palm oil (MEPO) were studied using a continuous flow-fixed bed reactor system at an atmospheric pressure. The catalyst was prepared by wet impregnation method with a solution of nickel nitrate hexahydrate as the precursor and zeolite as carrier. The characteristics of catalyst including active Ni metal content, crystallinity, total acidity, and porosity were evaluated. The reactions were performed with a varied hydrogen flow rate as a carrier gas as well as a reductant and reaction time. Liquid products were analyzed by GC. Analysis by GC-MS was only conducted on a product at hydrogen flow rate with the best conversion. It has been shown that the catalyst has a superior character for hydrocracking reactions of MEPO into green fuel. No considerable effect of hydrogen flow rate on the total conversion was observed. The tests showed that the kinetics of Ni/zeolite-catalyzed cracking reaction followed pseudo-first order kinetics. GC-MS analysis revealed the formation of light hydrocarbon products with C6-C8 of aliphatic and cyclic
components without oxygenates. Distribution of the product indicated that the cracking reaction as well as the isomerization of the products of hydrocracking occurred. Thus, Ni/zeolite-catalyzed cracking involved cracking /hydrogenation, isomerization, cyclization, and deoxygenation.
Keywordskinetics; mechanism; palm oil; bio-fuel
ABSTRAK
Kinetika dan mekanisme reaksi perengkahan methyl ester palm oil (MEPO) terkatalisis Ni/zeolite dipelajari dengan reaktor sistem continuous flow-fixed bed pada tekanan atmosfer. Katalis dipreparasi menggunakan metode impregnasi basah dengan larutan nikel nitrat heksahidrat sebagai prekursor dan zeolit sebagai pengemban. Karakteristik katalis yang meliputi kandungan logam aktif Ni, kristalinitas, keasaman total, dan porositas katalis telah dievaluasi. Reaksi dilakukan dengan laju alir hidrogen sebagai gas pembawa sekaligus sebagai reaktan dan waktu reaksi. Produk cair dianalisis dengan GC. Analisis dengan GC-MS hanya dilakukan terhadap product pada laju alir hidrogen dengan konversi terbaik. Telah ditunjukkan bahwa katalis memiliki karakter unggul untuk reaksi hidrorengkah MEPO menjadi bahan bakar nabati. Tidak teramati efek yang signifikan laju alir hidrogen pada konversi total. Hasil uji menunjukkan bahwa kinetika reaksi perengkahan MEPO terkatalisis Ni/zeolite mengikuti kinetika reaksi order satu semu. Analisis GC-MS menunjukkan pembentukan produk hidrokarbon ringan dengan komponen C6-C8 alifatik dan siklik tanpa komponen oksigenat. Distribusi produk menunjukkan bahwa reaksi baik
perengkahan dan isomerisasi produk hidroorengkah terjadi. Dengan demikian, reaksi perengkahan MEPO terkatalisis Ni/zeolitemelibatkan perengkahan/hidrogenasi, isomerisasi, siklisasi, dan deoksigenasi.
Kata Kuncikinetika; mekanisme; minyak sawit; bahan bakar nabati
INTRODUCTION
릤릤牨릤 릤릤䘐산릤릤릤갬䀸ꮠ䬬릤䬬䬬릤ꮠ산 산갬䘐ꮠ 릤릤릤ꮠ 릤䬬릤릤䬬산 ꮠ갬 ꮠꮠ릤䬬 산산䀸ꮠ산ꮠ갬 산ઈ산䬬릤ꮠ䬬릤갬릤산릤ꮠ䬬 산산ꮠ牨산 산䬬산䬬䬬䨸릤䬬 ꮠ산䀸갬䀸릤苨ꮠ䬬산 산䨸산산릤산ꮠ릤릤 ꮠɬ䨸릤ꮠ 릤䨸ꮠ ꮠɬ䨸ꮠ
⟴ꮠ﵌산산䘐산ꮠ릤산
EXPERIMENTAL SECTION
Preparation of catalysts
⟴ꮠ﵌산산䘐산ꮠ릤산
Characterization of catalysts
ꮠ릤ꮠ릤산산䀸䬬䘐산䬬 산산릤ꮠ릤䀸䨸䬬ꮠ갬
Catalytic cracking of MEPO with Ni/zeolite catalyst
苨릤갬산牨 ꮠ릤ꮠ릤산산䀸䬬䘐산䬬산릤ꮠ산
RESULT AND DISCUSSION
Characteristics of Ni/Zeolite Catalyst
Porosity of Ni/zeolite catalyst
산산산䀸ꮠ릤산ꮠ 릤산릤䘐릤릤 릤
Number of acid sites of Ni/zeolite catalyst
⟴ꮠ﵌산산䘐산ꮠ릤산
Ni content in Ni/zeolite catalyst
산䬬릤릤산갬䨸릤 산 릤ɬ䨸산ꮠ䀸 산산산䀸䬬ꮠ䬬
Crystallinity and particle size of Ni/zeolite catalyst 䀸䬬산ꮠꮠ䀸산산ꮠ릤䬬ꮠ릤 ꮠ릤ꮠ릤산산䀸䬬䬬
Catalytic Cracking of MEPO Catalyzed by Ni/Zeolite
⟴ꮠ﵌산산䘐산ꮠ릤산
Effect of reaction time to catalyst activity
⟴ꮠ﵌산산䘐산ꮠ릤산
GC-MS Analysis and Hypothetical Mechanism
⟴ꮠ﵌산산䘐산ꮠ릤산
Fig 5. 릤산ꮠ牨릤 산ꮠ䬬牨䬬 ꮠ릤ꮠ릤ઈ산산䀸릤 䀸산ꮠ갬 સ魤鯈ꮠꮠઈ 䨸릤산릤 牨산䬬ꮠꮠ릤산
ퟰ㮴
牨ꮠ산릤 ꮠ䬬산산 ꮠꮠ牨䨸䬬 산ઈ산산 ꮠꮠ 牨䨸䬬ꮠꮠ갬산䬬ꮠ릤 산ꮠ ꮠ䬬ꮠ䬬牨산릤 䬬䬬ꮠ릤䀸 릤산ꮠꮠ䀸 릤ꮠ릤䬬산산䀸릤 릤 ꮠ䬬牨릤ꮠ산ꮠ릤산ꮠ牨산릤산 릤산ꮠ릤䬬䨸 산䬬산䨸牨ꮠ산ퟰ뀨㮴苨牨산ꮠ䬬䨸䬬䘐 ꮠ 䨸䬬䨸산䀸 牨ꮠ산릤 릤산산䀸릤 䀸산ꮠ갬 산牨ꮠ산䬬 릤릤⟴ꮠ릤갬산산苨牨ꮠퟰ㮴ꮠ 산릤 ꮠ䬬 䬬䨸䀸䀸䬬산䨸산릤䀸ꮠ䨸䬬䘐릤릤 䨸 ꮠ䬬ꮠ䬬 릤산䨸䬬릤 릤 산ꮠ갬 릤산ꮠ 䘐ꮠ 릤ꮠ릤ઈ산䬬릤 산산䀸䬬 산 산牨牨산릤 ꮠ䬬牨릤ꮠ산ꮠ 릤산ꮠ䬬 산ꮠ갬산䀸ꮠ산ꮠ䬬ꮠ牨䨸산릤䨸䬬䀸ퟰ뀨㮴
⟴ꮠ﵌산산䘐산ꮠ릤산
Bioresour. Technol.,뀨ퟰퟰ왌ퟰ
산䀸산苨왌Biodiesel from Rape Seed Oil
and Used Frying Oil in European Union
릤ꮠ䨸䬬䬬ꮠ䨸릤쀔ꮠ릤䬬ꮠ릤ꮠ쀔릤
왌 릤牨ꮠ산䬬苨왌Energy Sources뀨뀨Ὠ
䘐산ꮠɬ苨산ꮠꮠ苨સ산 산ꮠ산⟴왌
Microporous Mesoporous Mater.ퟰઈ왌牐뀨ퟰ
뀨 ⟴산갬鯈�왌Energy Sources뀨牐뀨牐
Seminar Nasional Kimia dan Pendidikan Kimia III ⟴牐Ὠઈ牐Ὠ牐ઈퟰ뀨왌왌ઈ뀨ઈ牐Ὠ왌
ퟰ⟴ 릤릤 ퟰ牐ퟰMathematisch-Physikalische
Klasse, 2牐ퟰ
ퟰퟰસ릤산릤산䬬ퟰ牐ퟰKinetics
and Mechanisms 왌魤 ꮠ릤䀸산⟴䬬
⟴ꮠ﵌산산䘐산ꮠ릤산
ퟰꮠ䬬䨸산䀸산ꮠꮠ䘐산 䀸䨸ꮠ魤산⟴䨸ꮠ⟴
뀨Teknoinퟰ牐
ퟰ왌산릤ꮠસ갬䨸䀸릤⟴릤 릤䬬릤릤릤䬬
산⟴릤䬬 산﵌ퟰBioresour. Technol. ퟰퟰ
왌Ὠ왌ퟰ
ퟰસ릤䬬산⟴﵌સ䀸릤䬬સ산릤ꮠ
⟴牐Energy Fuels왌뀨牐뀨牐牐
ퟰ뀨⟴릤ઈ䀸䬬ꮠ䨸�산સꮠ䘐산ퟰퟰInd.
Eng. Chem. Res.뀨뀨Ὠ牐ퟰὨ牐牐
ퟰ⟴ꮠ릤갬산 산 苨牨ꮠ 苨⟴ Jurnal
Teknologi牐
ퟰὨꮠ산산苨સ산䘐산ꮠ苨산산䬬ꮠꮠસ
Makara J. Technol. Ser.ퟰ뀨ퟰ
ퟰ산䬬ꮠꮠસ⟴䨸䬬산ꮠ䬬산牨산સ苨산 ꮠ산산苨牐World Appl. Sci. J., 5ὨὨ牐 ퟰ牐릤牨鯈﵌산ꮠ산릤ꮠ⟴산산 䬬ꮠ
ퟰ牐牐ὨFuel Process. Technol.뀨ퟰퟰퟰퟰ뀨
ꮠ䬬䨸산䀸산ꮠꮠ䀸산ꮠꮠ산苨왌
Indo. J. Chem.왌牐
