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LAPORAN KEMAJUAN
PENELITIAN HI-IMPACT
DANA ITS 2020
(Biojetfuel Range Alkanes Production From Minyak Kemiri Sunan
(Reutealiss trisperm Oil) Via Hydrodeoxygenation Reaction By
Metal/Aluminosilicates From Local Source)
Tim Peneliti :
Prof. Didik Prasetyoko, M.Sc (Kimia/FSAD)
Dr. Yuly Kusumawati, M.Si (Kimia/FSAD)
DIREKTORAT RISET DAN PENGABDIAN KEPADA MASYARAKAT
INSTITUT TEKNOLOGI SEPULUH NOPEMBER
SURABAYA
2020
Sesuai Surat Perjanjian Pelaksanaan Penelitian No: 836/PKS/ITS/2020
i
Daftar Isi
Daftar Isi .......................................................................................................................................................... i
Daftar Tabel .................................................................................................................................................... ii
Daftar Gambar ............................................................................................................................................... iii
Daftar Lampiran ............................................................................................................................................. iv
BAB I RINGKASAN ..................................................................................................................................... 1
BAB II HASIL PENELITIAN ........................................................................................................................ 3
BAB III STATUS LUARAN ........................................................................................................................ 10
BAB IV PERAN MITRA (UntukPenelitian Kerjasama Antar Perguruan Tinggi) ...................................... 11
BAB V KENDALA PELAKSANAAN PENELITIAN ............................................................................... 12
BAB VI RENCANA TAHAPAN SELANJUTNYA ................................................................................... 13
BAB VII DAFTAR PUSTAKA ................................................................................................................... 14
BAB VIII LAMPIRAN ................................................................................................................................. 15
LAMPIRAN 1 Tabel Daftar Luaran ............................................................................................................. 46
ii
Daftar Tabel
iii
Daftar Gambar
Hal
Gambar 1. Spektra IR katalis aluminosilikat dari redmud (a) aluminosilikat H+-
Ni, (b) aluminosilikat H+, (c) aluminosilikat Na+Ni, (d) aluminosilikat
Na+
4
Gambar 2. Difraktogram katalis aluminosilikat dari redmud (a) aluminosilikat H+-
Ni, (b) aluminosilikat H+, (c) aluminosilikat Na+Ni, (d) aluminosilikat
Na+
5
Gambar 3. N2 adsorpsi-desorpsi katalis aluminosilikat redmud (a) dan distribusi
ukuran pori menggunakan metode DFT (b)
6
Gambar 4. Foto TEM katalis aluminosilikat redmud
6
Gambar 5. Komposisi Produk Biojetfuel Minyak Kemiri Sunan dengan Reaksi
Hidrodeoksigenasi menggunakan katalis Aluminosilikat redmud
7
Gambar 6. Distribusi Produk Biojetfuel Minyak Kemiri Sunan dengan Reaksi
Hidrodeoksigenasi menggunakan katalis Aluminosilikat redmud
7
iv
Daftar Lampiran
Lampiran 1 . Abstrak Submitted pada Seminar ICCME 2020…………………………………
Lampiran 2. Draft paper publikasi jurnal internasional ……………………………………….
1
BAB I RINGKASAN
.
Penelitian yang dilakukan memiliki tujuan untuk menghasilkan produk senyawa alkana
dalam range bio jet-fuel dari bahan baku minyak nabati non-edible Kemiri Sunan (Reutealis
trisperm) menggunakan material katalis aluminosilikat dari sumber alam lokal dalam rangka
mendukung subtitusi bahan bakar yang berkelanjutan. Bio jet-fuel dari konversi minyak nabati
non-edible Reutealis trisperm atau Kemiri Sunan merupakan alternatif pengganti bahan bakar
fosil yang potensial untuk dikembangkan karena faktor kelimpahan yang tinggi dan tidak
menimbulkan persaingan dengan sektor pangan dan pertanian. Dengan meningkatnya
kebutuhan energi dalam bidang transportasi dari tahun ke tahun, mengakibatkan penelitian
tentang teknologi subtitusi bahan bakar maupun pengembangan material maju sebagai katalis
reaksi konversi minyak nabati menjadi bio jet-fuel menjadi perhatian banyak peneliti.
Peningkatan performa bahan bakar jenis biodiesel menjadi bio jet-fuel karena keunggulan sifat
fisik dan kimianya untuk aplikasi pada mesin kendaraan darat dan udara, melibatkan
penggunaan katalis yang spesifik dan selektif dalam reaksi konversi energi baru terbarukan.
Inovasi modifikasi katalis konversi untuk menghasilkan senyawa hidrokarbon alkana
dalam range bio jet-fuel sangat berperan untuk mencapai hasil akhir reaksi konversi katalitik
dengan tingkat selektifitas dan konversi yang tinggi. Dalam usulan penelitian ini modifikasi
permukaan katalis aluminosilikat dilakukan dengan penambahan logam aktif nikel dan kobalt
serta variasi interaksi logam dan support dalam framework aluminosilikat. Material
aluminosilikat dalam penelitian ini disintesis dari sumber alam lokal seperti limbah bauksit (Red
mud) dan kaolin juga merupakan keterbaruan dalam penelitian produksi bio jet-fuel melalui
reaksi hidrodeoksigenasi. Selain itu pemanfaatan limbah bauksit juga menjadi salah satu solusi
permasalahan lingkungan yang dapat diintegrasikan dengan pemngembangan material untuk
energi dan lingkungan.
Sintesis aluminosilikat dilakukan dengan metode hidrotermal dengan tahapan dua kali
kristalisasi (two steps crystallization) melalui proses alkali fusi yang ditambahkan dengan
logam aktif Ni dan Cu sebagai katalis reaksi hidrodeoksigenasi minyak Kemiri Sunan.
Karakterisasi fisika dan kimia katalis dalam penelitian ini dilakukan dalam rangka mengetahui
efektivitas dan selektivitas katalis berbasis sumber lokal pada produksi senyawa alkana dalam
range bio jet-fuel. Uji katalitik reaksi hidrodeoksigenasi selanjutnya dilakukan dalam skala
laboratorium menggunakan feedstock minyak Kemiri Sunan dalam reaktor batch dengan variasi
2
parameter reaksi jenis katalis, suhu dan waktu reaksi untuk mendapatkan data tentang konversi
dan selectivitas produk senyawa alkana range bio jet-fuel.
Luaran yang ditargetkan dalam penelitian ini yaitu artikel ilmiah yang disubmit pada jurnal
internasional teindeks Scopus Q1 yaitu Journal of The Energy Institute dengan H Index Jurnal 31,
Impact factor 3,774, citation score 4,10 dan luaran tambahan adalah seminar internasional.
3
Ringkasan penelitian berisi latar belakang penelitian,tujuan dan tahapan metode
penelitian, luaran yang ditargetkan, kata kunci
BAB II HASIL PENELITIAN
Hasil penelitian yang telah dilakukan meliputi sintesis katalis aluminosilikat berbasis
sumber lokal red mud/kaolin, karakterisasi katalis aluminosilikat, uji aktivitas katalis melalui reaksi
hidrodeoksigenasi minyak kemiri sunan.
1. Sintesis aluminosilikat
Sintesis aluminosilikat dengan sumber alumina redmud pulau Bintan dilakukan dengan metode
hidrotermal melalui 2 tahap kristalisasi pada suhu 80 °C selama 24 jam dan 28 °C selama 4 jam serta dan
sumber silika kaolin Bangka Belitung yang dilakukan dengan metode hidrotermal melalui 2 tahap kristalisasi
pada suhu 80 °C selama 12 jam dan 150 °C selama 24 jam . Padatan aluminosilikat yang terbentuk
selanjutnya dicuci dengan aquades hingga pH netral. Katalis aluminosilikat selanjutnya dilakukan proses
kalsinasi untuk menghilangkan template CTABr yang berperan dalam proses pembentukan mesopori. Katalis
yang terbentuk selanjutnya dimodifikasi struktur permukaannya untuk mengetahui sisi aktif yang berperan
dalam reaksi hidrodeoksigenasi melalui beberapa cara yaitu impregnasi logam Ni menghasilkan katalis
aluminosilikat bentuk Na+-Ni, pertukaran kation Na+ pada aluminosilikat dengan H+ menghasilkan katalis
aluminosilikat H+, serta pertukaran kation dan impregnasi logam Ni menghasilkan katalis aluminosilikat H+-
Ni. Masing-masing katalis selanjutnya dikarakterisasi menggunakan FTIR, XRD, N2 adsorpsi-desorpsi,
TEM.
Modifikasi sintesis aluminosilikat selanjutnya dilakukan untuk meningkatkan luas mesopori dan
terbentuknya pori intrapartikel yang teratur seperti Al-MCM-41. Sintesis dilakukan dengan rasio molar
10Na2O:xSiO2: 2Al2O3:1800H2O, dimana x adalah 60, 100, 140 dan 180 Penambahan CTABr dilakukan
sebagai template mesopori. Kaolin Bangka Belitung digunakan sebagai sumber silika dan alumina dalam
sintesis Al-MCM-41. Sintesis dilakukan dengan dua tahap kristalisasi yakni pada temperatur 80 ℃ selama
12 jam dan 150 ℃ selama 24 jam. Padatan selanjutnya dicuci dengan aqudes hingga pH netral dan
dikeringkan pada temperatur 60 ℃ selama 24 jam. Padatan dikalsinasi pada temperatur 550 ℃ dengan
kecepatan pemanasan 2℃/menit menggunakan aliran gas N2 selama 1 jam dan aliran udara selama 6 jam.
Katalis selanjutnya ditukar kation menggunakan ammonium asetat untuk menukar kation Na+ menjadi H+.
Katalis dikarakterisasi menggunakan XRD.
2. Karakterisasi FTIR
Katalis aluminosilikat dikarakterisasi dengan FTIR untuk mengetahui gugus fungsional dari material
yang telah disintesis. Gambar 1 menunjukkan spektra FTIR dari katalis aluminosilikat awal dan yang telah
dimodifikasi struktur permukaannya. Seluruh katalis yang telah disintesis menunjukkan puncak serapan
karakteristik dari aluminosilikat, yaitu puncak serapan pada bilangan gelombang 3452, 3525, dan 3622
cm-1 yang merupakan puncak serapan khas dari vibrasi ulur –OH [1], sedangkan puncak serapan
4
pada bilangan gelombang 1629 cm-1 menandakan adanya vibrasi tekuk –OH. Puncak serapan khas
untuk vibrasi tekuk Si-O-Si, dan Si-O-Al terlihat pada daerah bilangan gelombang 1012, dan 1031
cm-1. Vibrasi ulur Si-O pada tetrahedral SiO4 menunjukkan puncak serapan pada bilangan
gelombang 746, 798, dan 914 cm-1 [2]. Puncak serapan pada bilangan gelombang 450 cm-1 yang
dihasilkan karena adanya vibrasi ikatan T-O-T (T adalah atom Al atau Si). Pada bilangan gelombang 550
cm-1 menunjukkan adanya vibrasi stretching asimetri dari D5R (double five-membered ring) yang merupakan
karakteristik dari struktur zeolite pentasil tipe MFI. Sedangkan pada bilangan gelombang 795 dan 1225 cm-
1 merupakan vibrasi streching eksternal simetri dan asimetri dari T-O-T.
Gambar 1. Spektra IR katalis aluminosilikat dari redmud (a) aluminosilikat H+-Ni, (b) aluminosilikat H+,
(c) aluminosilikat Na+Ni, (d) aluminosilikat Na+
3. Karakterisasi XRD
Katalis aluminosilikat dikarakterisasi menggunakan XRD untuk mengetahui fasa yang terbentuk dari
material yang telah disintesis. Gambar 2 menunjukkan difraktogram dari katalis yang telah disintesis. Pola
difraktogram pada aluminasilika hasil sintesis (ASM) menunjukkan adanya hump (gundukan) pada
range 2θ = 15-30° tanpa adanya puncak. Menurut Xu dkk., (2011) adanya hump merupakan
karakteristik dari fasa amorf suatu padatan, sehingga dapat disimpulkan bahwa ASM hasil sintesis
memiliki fasa amorf [3]. Hasil yang sama juga dilaporkan oleh Qoniah dkk., [4]); dan Hartati,
a
b
c
d
5
Prasetyoko, dkk., [5]. Berdasarkan hasil tersebut, dapat disimpulkan bahwa ASM telah berhasil
disintesis dari red mud dan fasa yang dihasilkan adalah amorf.
Gambar 2. Difraktogram katalis aluminosilikat dari redmud (a) aluminosilikat H+-Ni, (b) aluminosilikat H+,
(c) aluminosilikat Na+Ni, (d) aluminosilikat Na+
Al-MCM-41 yang telah disintesis dengan variasi rasio Si/Al selanjutnya dikarakterisasi menggunakan XRD
seperti yang ditampilkan pada Gambar 3. Difraktogram Al-MCM-41 (Si/Al= 10) menunjukkan terbentuknya
kristalin material dengan intensitas yang tajam pada 2θ= 12,15; 17,66; 21,32; 27,83 dan 33⁰. Hasil analisis
menggunakan software match menunjukkan Terbentuknya fasa Quartz, SiO2 dan kristobalit. Hal ini
menunjukkan bahwa fase amorf dari Al-MCM-41 tidak terbentuk pada rasio Si/Al=10. Selanjutnya pada Al-
MCM-41 dengan variasi Si/Al= 30, 50, 70 dan 90 menunjukkan terbentuknya hump/gundukan pada 2θ= 15-
30⁰ yang merupakan karakteristik dari aluminosilikat amorf.
a
b
c
d
6
Gambar 3. Difraktogram Al-MCM-41 dengan variasi Si/Al
4. Karakterisasi N2 adsorpsi-desorpsi
Karakterisasi menggunakan N2 adsorpsi-desorpsi dilakukan pada sampel katalis aluminosilikat dari redmud
awal. Karakterisasi ini bertujuan untuk mengetahui sifat textural dari material yang telah disintesis seperti
luas permukaan meso, mikro, ukuran pori dan volume pori. Gambar 4 menunjukkan grafik isoterm dan
distribusi ukuran pori katalis aluminosilikat. Pola isoterm ASM hasil sintesis menunjukkan pola isoterm
tipe IV dimana terjadi adsorpsi molekul nitrogen dalam jumlah rendah pada tekanan relatif (P/P0)
0,0 sampai 0,3 yang ditandai dengan pola isoterm yang naik. Hal ini disebabkan pada tekanan relatif
0,01 – 0,3 molekul nitrogen yang teradsorp memenuhi permukaan padatan sehingga terbentuk
lapisan tunggal atau monolayer. Pada tekanan relatif (P/P0) 0,4 – 0,9 mengindikasikan terbentuknya
multilayer dengan adanya penambahan volume molekul nitrogen yang teradsorpsi (Chorkendorff
dan Niemantsverdriet, 2017). Data distribusi ukuran pori dari sampel aluminosilikat mesorpori
dengan metode BJH (Barret, Joiner, Halenda). Berdasarkan gambar tersebut terlihat bahwa
7
distribusi pori sampel aluminosilikat memiliki ukuran pori pada radius sekitar 1,53 – 15,57 nm
(diameter pori 3,1 – 31 nm) (Tabel 4.2) dengan luas permukaan total 404 m2/g.
Gambar 4. N2 adsorpsi-desorpsi katalis aluminosilikat redmud (a) dan distribusi ukuran pori menggunakan
metode DFT (b)
Berdasarkan analisis N2 adsorpsi- desorpsi dapat dsimpulkan bahwa katalis aluminosilikat dari
sumber redmud memiliki karakteristik padatan mesopri interpartikel.
5. Karakterisasi TEM
Karakterisasi TEM pada katalis aluminosilikat dilakukan untuk mengetahui sebaran pori meso dan
ukuran pori katalis. Gambar 5 menunjukkan hasil foto TEM katalis aluminosilikat dari redmud.
Berdasarkan gambar TEM terlihat bahwa pori dari ASM memiliki bentuk pori spherical dan tidak
teratur dengan ukuran pori ~1 nm. Hal ini dapat dilihat dari pembentukan sistem penghubung yang
terjadi secara acak. Hasil yang sama juga dilaporkan oleh Qoniah dkk., (2015) dimana dihasilkan
aluminosilikat dengan bentuk pori yang tidak teratur pada material aluminosilikat. Hasil analisa
TEM ini juga mengkonfirmasi adanya mesopori yang terbentuk pada interpartikel.
8
Gambar 5. Foto TEM katalis aluminosilikat redmud
6. Uji Aktivitas Katalitik dengan Minyak Kemiri Sunan
Uji aktivitas katalitik katalis aluminosilikat dilakukan pada reaksi hidrodeoksigenasi minyak kemiri
sunan dengan kondisi reaksi 3% katalis, temperatur reaksi 300 oC, waktu reaksi 1 jam, dan aliran gas
hydrogen 50 dan 100 mL/menit sebagai studi pendahuluan. Hasil analisis biojetfuel dari reaksi
hidrodeoksigenasi minyak kemiri sunan dengan instrument GC-MS menunjukkan hasil komposisi produk
biojetfuel meliputi, aromatic, siklik, oksigenate dan
Gambar 6. Komposisi Produk Biojetfuel Minyak Kemiri Sunan dengan Reaksi Hidrodeoksigenasi
menggunakan katalis Aluminosilikat redmud
9
Gambar 6. Distribusi Produk Biojetfuel Minyak Kemiri Sunan dengan Reaksi Hidrodeoksigenasi
menggunakan katalis Aluminosilikat redmud
Berdasarkan hasil analisis terhadap aktivitas katalitik katalis aluminosilikat dari sumber alam,
menunjukkan bahwa hasil produk biojetfuel yang dihasilkan didominasi oleh senyawa aromatic yang
sesuai dengan karakter jet fuel yang ditetapkan oleh IATA dan standar jet A. Komposisi senyawa
aromatic telah memenuhi range standar senyawa aromatic untuk jetfuel. Oleh karena itu penelitian ini
memiliki potensi untuk pengembangan biojetfuel dari minyak kemiri sunan menggunakan katalis
aluminosilikat berbasis sumber alam lokal.
10
BAB III STATUS LUARAN
Status luaran yang ditargetkan pada penelitian ini yaitu luaran wajib pada jurnal ilmiah internasional
masih dalam penyelesaian data dan tahap penyusunan draft artikel. Luaran tambahan yaitu seminar
internasional akan dilaksanakan pada 6-7 Oktober 2020 pada forum ICCME 2020 (The 4th International
Chemical Conference on Material and Engineering) yang diselenggarakan oleh Universitas Diponegoro
(UNDIP)
11
BAB IV PERAN MITRA (UntukPenelitian Kerjasama Antar Perguruan Tinggi)
Penelitian ini tidak memiliki mitra.
12
BAB V KENDALA PELAKSANAAN PENELITIAN
Kendala yang dihadapi selama pelaksanaan penelitian adalah adanya pandemi Covid-19 di Indonesia
yang menyebabkan kegiatan penelitian di laboratorium sedikit terhambat dan terkendala layanan analisis
instrument untuk karakterisasi material dan uji aktivitas katalitik yang belum beroperasi maksimal sehingga
data eksperimen belum mencapai target. Hambatan lainnya yaitu keterbatasan alat yang digunakan untuk
reaksi hidrodeoksigenasi yang membuthkan waktu lama untuk membuat reaktor. Lamanya waktu yang
diperlukan untuk analisa material, hal ini dikarenakan terbatasnya jumlah instrument analisis material di
Indonesia untuk karakterisasi seperti N2 adsorpsi desorpsi dan TEM, banyaknya antrian menyebabkan waktu
yang diperlukan untuk analisis menjadi lama. Karakterisasi material menggunakn N2 adsorpsi dilakukan di
UII dan ITS diperlukan waktu 1-2 bulan. Karakterisasi material menggunakan TEM di Indonesia hanya bisa
dilakukan di ITB, waktu tunggu hingga mendapat jadwal karakterisasi antara 2 minggu – 1 bulan. Penelitian
tentang produksi biojetfuel dari minyak kemiri sunan ini termasuk topik penelitian baru di dalam Grup Riset
Material dan Energi, sehingga diperlukan setting alat dan pemahaman mengenai desain dan rangkaian
reaktor. Banyak kendala yang dialami dalam tahapan ini, diantaranya kesulitan dalam menyusun rangkaian
alat hingga kendala kebocoran gas.Kesulitan lain yang dihadapi adalah dalam penulisan paper publikasi,
dikarenakan kurangnya media yang dapat memfasilitasi dalam penulisan artikel ilmiah yang baik.
13
BAB VI RENCANA TAHAPAN SELANJUTNYA
Rencana tahapan penelitian selanjutnya adalah melanjutkan sintesis katalis dari sumber kaolin serta
uji aktivitas katalitik enggunakan minyak kemiri sunan dengan variasi parameter kondisi reaksi yang
berbeda. Selain itu juga akan dilakukan penyempurnaan penyusunan draf artikel imiah untuk publikasi pada
jurnal internasional .
14
BAB VII DAFTAR PUSTAKA
1. Sushil, S., dan Batra, V.S. (2012), “Modification of Red Mud by Acid Treatment and Its
Application for CO Removal.” Journal of Hazardous Materials, Vol. 203–204, No.
Februari, Hal. 264–273
2. Liu, W., Yang, J., dan Xiao, B. (2009), “Application of Bayer Red Mud for Iron Recovery
and Building Material Production from Alumosilicate Residues.” Journal of Hazardous
Materials, Vol. 161, No. 1, Hal. 474–78.
3. Xu, L., Liu, Z., Li, Z., Liu, J., Ma, Y., Guan, J., dan Kan, Q. (2011), “Non-Crystalline
Mesoporous Aluminosilicates Catalysts: Synthesis, Characterization and Catalytic
Applications.” Journal of Non-Crystalline Solids, Vol. 357, No. 4, Hal. 1335–1341.
4. Qoniah, I., Prasetyoko, D., Bahruji, H., Triwahyono, S., Jalil, A.A., Suprapto, Hartati, dan
Purbaningtias, T.E. (2015), “Direct Synthesis of Mesoporous Aluminosilicates from
Indonesian Kaolin Clay without Calcination.” Applied Clay Science, Vol. 118, No.
Desember, Hal. 290–294.
5. Hartati, Didik Prasetyoko, Mardi Santoso, Hasliza Bahruji, dan Sugeng Triwahyono (2014),
“Highly Active Aluminosilicates with a Hierarchical Porous Structure for Acetalization of
3,4-Dimethoxybenzaldehyde.” Jurnal Teknologi (Science & Engineering, Vol., Mei, Hal,
25–30
15
BAB VIII LAMPIRAN
1. Abstrak tersubmit pada ICCME
Mmllml
Biojetfuel Production From Reutealis Trisperm Oil Over Indonesian Red Mud Based
Catalyst
D. Prasetyoko a*, D.K.Maharani a, Y. Kusumawati a
a Department of Chemistry, Faculty of Science and Analytical Data, Sepuluh Nopember Institute of
Technology , Surabaya, East Java, 59323, Indonesia. (Email:[email protected];
[email protected]; [email protected]; [email protected]
*Corresponding author
D.Prasetyoko, Department of Chemistry, Faculty of Science and Analytical Data, Sepuluh Nopember
Institute of Technology, Surabaya, East Java, 59323, Indonesia. (Email: [email protected])
Abstract
Redmud is one of caustic waste generated from by product of alumina by production. Composition
of redmud are Fe2O3, SiO2, Al2O3, TiO2 and other minor components [1-3]. Indonesian redmud
has been studied for hydrodeoxygenation reaction (HDO) of Reutalis trisperm oil which is non-
edible feedstock as potential catalyst for bio jet-fuel production. Aluminosilicates were synthesized
from Indonesian redmud has mesoporous structure with uniform particle size as confirmed by
TEM image and nitrogen adsorption isotherm data. Catalytic study of aluminosilicates mesopore
on HDO of Reutealis trisperm oil resulted in jetfuel range liquid product consist of hydrocarbon,
aromatic, cyclic and oxygenates component. Change in HDO liquid product composition were
confirmed on different structure of aluminosilicates mesopore form. At H+ form of aluminosilicates
mesopore catalyst, oxygenates product yield were 54.1% indicating slight decreased compared
to that 66.1% Na form. Ni loading on aluminosilicates mesopore of H+ form increase the aromatic
product into 31.8% and also reduce oxygenates content. This result was in accordance with
previouse study that state increasing Ni loading on redmud catalyst produced higher hydrocarbon
component in HDO of Pinyon janiper oil. Aromatic content in biojetfuel produced from this
research was fulfill the standart of JetA (ASTM) and JetA (IATA) which mean it has a possibility
for jet fuel commercial uses.
Keywords: biojetfuel; hydrodeoxygenation; redmud; aluminosilicates mesopore; Reutealis
trisperm oil
Fig.1. TEM images of Aluminosilicates mesopores synthesized from Indonesian Redmud .
ICCME 2020 Abstract Template
16
Fig.2. Liquid product distribution from HDO reactionof Reutealis of trisperm oil with different
Aluminosilicates mesopores catalysts at temperature of 300 oC and time of 1 h.
Fig.3. Hydrocarbon composition of liquid product by various Aluminosilicate mesopore catalyst
from HDO reaction of Reutealis trisperm Oil
Table 1. Nitrogen Adsorption Isotherm Data of Aluminosilicate mesopores
17
2. Draft Paper
Solvent-free selective deoxygenation of Jatropha Curcas oil to green diesel on Al-MCM-41 from kaolin
with suppressed hydrocracking activity
Reva Edra Nugraha1, Nurul Asikin-Mijan2, Suprapto Suprapto1, Yun Hin Taufiq-Yap3,4, Aishah Abdul
Jalil5,6, Hasliza Bahruji7, Didik Prasetyoko1,*
1Department of Chemistry, Faculty of Sciences, Institut Teknologi Sepuluh Nopember, Keputih Sukolilo,
Surabaya 60111, Indonesia
2Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia,
43600 UKM Bangi, Selangor, Malaysia
3Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor,
Malaysia
4Chancellery Office, Universiti Malaysia Sabah, 88400, Kota Kinabalu, Sabah
5Department of Chemical Engineering, Faculty of Chemical and Energy Engineering, Universiti Teknologi
Malaysia, 81310, Skudai, Johor Bahru, Johor, Malaysia
6Centre of Hydrogen Energy, Institute of Future Energy, Universiti Teknologi Malaysia, 81310, Skudai,
Johor Bahru, Johor, Malaysia
7Centre of Advanced Material and Energy Sciences, Universiti Brunei Darussalam, Jalan Tungku Link, BE
1410, Brunei
*Corresponding author: [email protected]; [email protected]
Abstract
Solvent-free selective deoxygenation of Jatropha Curcas oil (JCO) provides a green catalytic pathway for
conversion of non-edible oil into value added green diesel. Selective deoxygenation reaction was carried out
in N2 using porous aluminosilicate as acid catalysts. Hierarchical ZSM-5 and Al-MCM-41 were synthesised
from kaolin at similar Si/Al ratios. The effect of mesoporosity, pore structure and acidity of aluminosilicate
catalysts were investigated on the conversion and the selectivity towards long-chain (C11-C18) hydrocarbon.
JCO deoxygenation reaction occurred via decarboxylation/decarbonylation pathway. Deoxygenation was
also in competition with hydrocracking reaction that produced short-chain hydrocarbons (C8-C10). This study
18
demonstrates the importance of high strength Lewis acidity and one-dimensional mesopores channel of Al-
MCM-41 to enhance the mass transfer and the diffusion of products/reactant in order to increase conversion
and to suppress the secondary hydrocracking reaction. Although hierarchical ZSM-5 contained mesopores
with parallel pore channel, the low concentration of Lewis acidity reduced the JCO conversion.
Keyword: ZSM-5, Al-MCM-41, deoxygenation, hydrocarbon, kaolin
1. Introduction
Development of renewable energy is recognised as route to fulfil the increasing energy demand and to tackle
the environmental issue associated with the fossil fuel consumption. Integrated catalytic conversion of
biomass as carbon feedstock to fuel has received tremendous attention since the development of the first
generation biodiesel in 2008 [1]. Biodiesel is consisted of fatty acid methyl ester (FAME) produced from
transesterification reaction of oil from plant or animal [2]. However, FAME consisted of high oxygen content
that contributed to the low heat value of biodiesel (HV) [3–7]. Biodiesel also exhibited poor oxidation and
cold-flow properties that affected the performance in the conventional engine [8,9]. Green diesel with
petrodiesel-like structures with C12-22 of hydrocarbons composition exhibits enhanced properties than
biodiesel [1]. Green diesel was produced from deoxygenation reaction via elimination of carboxyl group in
fatty acid. The reaction occurred under H2-free atmosphere and produced hydrocarbon with one atom carbon
shorter than the corresponded fatty acid (C(n-1)) [10,11]. Jathropa curcas oil (JCO) as non-edible oil can be
cultivated on marginal land with low rainfall areas, and showed high durability to withstand pest and drought
[12]. JCO is consisted of saturated and unsaturated long chain fatty acids that was ideal for deoxygenation
to green diesel [13,14]. Deoxygenation reaction were often performed in the presence of organic solvent like
decalin, dodecane, hexane and methanol [13,15–19]. Solvent free deoxygenation reaction reduced the cost
of product purification and waste disposal. Activated carbon [4,20], multi-walled carbon nanotube
(MWCNT) [10,16,21], mesoporous SiO2 [22,23], mesoporous TiO2 [24,25], ZrO2 [26], CaO [3,27], Al2O3
[15], Al-MCM-41 [5,11,28], SBA-15 [1,29], ZIF-67 [30] and zeolites [2,31–35] have been investigated as
catalysts for deoxygenation reaction. However porous aluminosilicates catalysts such as zeolite and
mesoporous alumina/silica were the ideal candidates due to the synergistic effects between porosity and
acidity [35–38]. Microporous zeolite as catalysts for deoxygenation reaction suffered from steric hindrance
19
and diffusion limitation that reduced the accessibility of large molecules reactant towards the acid sites [39].
Hierarchical ZSM-5 zeolite exhibited two levels of porosity i.e. micropore and mesopore that enhanced the
diffusion and reduced the mass transfer limitation of products and reactants. Conventional method for the
synthesis of hierarchical zeolite employed the desilication or the dealumination of the microporous zeolite,
that often contributed to the destruction of zeolite framework and altered the acidity of the zeolite [40–43].
Two-step crystallization method with the presence of mesopore template provided efficient route for the
formation of hierarchical zeolite. Utilization of naturally occurring mineral as silica and alumina sources
such fly ash, rice husk and clay reduced the carbon footprint of catalyst production [44,45]. Clay minerals
like montmorilonite [46], palygorskite [47], bentonite [48], perlite [49], illite [50] and halloysite [51]
required pretreatment meanwhile kaolin can be directly used for synthesis aluminosilicate materials [52–54].
Kaolin is a sedimentary rock consisted of primarily a hydrated aluminosilicate kaolinite, Al4(OH)8(Si4O10)
with high Si/Al ratios and has been explored as starting material for zeolite synthesis [55].
Catalyst design holds the key for efficient deoxygenation of oil into green diesel. Deoxygenation reaction
required the catalysts to selectively produced hydrocarbon olefin through the removal of carbonyl group in
fatty acid, while simultaneously inhibited the secondary cracking reaction. Catalytic cracking reaction
produced short-chain hydrocarbon that compromised the selectivity towards large hydrocarbons. This
research aimed to investigate the activity of ZSM-5 and Al-MCM-41 toward deoxygenation of JCO in order
to form hydrocarbon with green diesel composition (C11-C18). Al-MCM-41 is a mesoporous aluminosilicate
consisted of one-dimensional cylindrical mesopores, synthesized using CTABr as mesopore template. The
effect of large mesopore and unidirectional channel of Al-MCM-41 was compared with microporous ZSM-
5 and hierarchical ZSM-5. ZSM-5 consists of zigzag pore channel with narrow intersection was synthesized
using TPAOH as template. Hierarchical ZSM-5 with enhanced mesoporosity was synthesized using silicate
as structure directing agent in order to increase the pore diameter that ideally will enhance the diffusion of
reactants and products. The competition between deoxygenation and secondary hydrocracking reactions
were correlated with the aluminosilicate framework structure, the mesoporosity and the acidity of the
catalysts.
2. Experimental
2.1 Materials
20
Kaolin Al4(OH)8(Si4O10) was obtained from Bangka Belitung consisted of 57% SiO2 and 22% Al2O3 [56].
Jatropha curcas oil (JCO) was purchased from Bionas Sdn Bhd, Malaysia. NaOH (assay 99%) was obtained
from Merck, Germany. LUDOX® HS-40 colloidal silica (30% silica in water) and TPAOH (40%) were
purchased from Sigma Aldrich, Germany. CTABr (C19H42BrN, assay 99%) was purchased from Applichem.
All materials used in this work were analytical grade. Silicalite was synthesized in the laboratory prior to
the ZSM-5 synthesis.
2.2 Synthesis of hierarchical aluminosilicate
Hierarchical ZSM-5 was synthesized following the modified method [57,58] at molar composition of
10Na2O:100SiO2: 2Al2O3:1800H2O. CTABr was added at SiO2/CTABr ratio of 3.85 in order to form
mesopore structure. NaOH was dissolved in demineralized water and stirred for 30 min. Kaolin as alumina
and silica sources was added gradually into NaOH with continuous stir. Ludox was added slowly into the
mixture to form gel under vigorous stirring. Demineralized water was added into the mixture and stirred for
another 8 h. The gel was left to age for 6 h at 70 ℃ followed by the addition of silicalite at 1% w/w to the
solution and stirred for another 30 min. The first hydrothermal process was carried out at 80 ℃ for 12 h and
then the autoclave was cooled down under water to stop the crystallization process. CTABr
(SiO2/CTABr=3.85) was added slowly to the synthesis mixture and stirred for 1 h. Hydrothermal process
was continued at 150 ℃ for 24 h. The resulting solid was washed thoroughly with distilled water until the
pH reached 7 and then dried in air oven at 60 ℃ for 24 h. The dried solid was then calcined at 550 ℃ under
N2 flow (flow rate of 2 ℃/min) for 1 h followed by air flow for 6 h. The catalyst obtained denoted as S-
ZSM-5. Similar procedure was repeated however silicalite was replaced with TPAOH and the product was
denoted as T-ZSM-5. The third sample was synthesized without the addition of both TPAOH and silicalite
seed, however following the similar method and denoted as Al-MCM-41.
2.3 Catalyst characterization
The phase transformation of kaolin to aluminosilicate structure was analysed by wide angle X-Ray
Diffraction (XRD) characterization using PHILIPS-binary XPert with MPD diffractometer with Cu Kα
radiation operated at 30 mA and 40 kV. Low angle X-Ray Diffraction (XRD) was carried out using Bruker
type D2 Phaser using KFL Cu 2K radiation at 10 mA and 30 kV. Fourier Transform Infra-Red (FTIR) (ranges
21
400 – 1400 cm-1) measurement was recorded using FTIR Shimadzu Instrument Spectrum One 8400S. The
specific surface area of each catalyst was determined by N2 Adsorption Desorption by Quantachrome
Touchwin v1.11 instrument at 363 K using Brunauer–Emmet–Teller (BET) method. The pore size
distributions further determined by DFT method using Quantachrome ASiQwin instrument. The Brønsted
and Lewis acidity were measured by pyridine adsorption using FTIR spectrometer. Approximately, 14 mg
of catalyst was pressed to form pellet and placed in the homemade glass transmmission cell and calcined at
400 °C for 4 h under N2 flow. The cooled to ambient temperature prior to contact with ca. 2 mbar of pyridine.
Physically adsorbed pyridine was removed by degassing at 150 ℃ for 3 h. The low resolution and high
resolution transmission electron microscope (TEM) images of all catalysts were recorded using Hitachi HT-
7700 TEM and Hitachi HR-9500 TEM. The acceleration voltage of 100 kV and 300 kV were applied at HT-
7700 TEM and Hitachi HR-9500 TEM respectively. The catalyst further analyzed using 29Si MAS NMR
coupled with Varian Unity INOVA 400 MHz spectrometer, at pulse length of 3.0 µs, recycle delay of 12 s
and spinning rate of 9 kHz. The Si/Al framework ratio were quantified from the integrated areas of the
deconvoluted peak by using Eq. 1
𝑆𝑖
𝐴𝑙= ∑ 𝐼𝑆𝑖(𝑛𝐴𝑙)/ ∑
𝑛
4[𝐼𝑆𝑖(𝑛𝐴𝑙)]4
𝑛=04𝑛=0
The carbonaceous coke formation on spent catalysts were determined using thermogravimetric analysis
(TGA) by Linseis STA PT-1000. The analysis was carried out under air atmosphere from room temperature
up to 900 ℃ with heating rate 10 ℃/min. The functional group and physical changes on spent catalyst also
further observed by FTIR and low angle XRD analysis. The analysis was conducted within IR range of 500-
4000 cm-1 and the resolution was 4 cm-1. Low angle-XRD was carried out using Bruker type D2 Phaser using
KFL Cu 2K radiation at 10 mA and 30 kV.
2.4 Catalytic deoxygenation of JCO
Deoxygenation reaction of JCO was performed in 100 mL three-necked flask connected with distillation
step-up equipped with stirred heating mantle. 3% wt/wt of catalyst was added into 10 g JCO and purged with
N2 gas prior to the reaction to provide inert environment during the reaction. Subsequently, the mixture was
stirred and heated to 350 ℃ and the reaction was maintained for 1 h under constant flow of N2 at flow rate
of 20 cc/min. Liquid product was collected in a cold vessel at 18 oC to facilitate the condensation. The
Eq. 1
22
deoxygenated liquid product was further analysed using GC-FID, GC-MS and FTIR spectroscopy. The
gaseous products were collected by gas sampling bag and analysed using offline GD-TCD (Shimadzu GC-
8 A) with molecular sieve packed column.
2.5 Deoxygenated liquid product and gas analysis
Liquid product obtained from deoxygenation reaction was analysed using gas chromatography equipped
with FID detector (Shimadzu GC-14B) and capillary column HP-5MS (length: 30 m × inner diameter: 0.32
mm × film thickness: 0.25 µm). Hydrocarbons were identified using alkane and alkene standard (C8-C20)
obtained from Sigma Aldrich, and 1-bromohexane was used as internal standard for the quantitative analysis.
1 µL of liquid sample was injected into GC column with N2 as carrier gas. The initial temperature was set
for 40 ℃ and held for 6 min, then increase to 270 ℃ at heating rate of 7 ℃. The liquid product distribution
was qualitatively identified using gas chromatography-mass spectroscopy (HP 6890 GC) with capillary
column HP-5MS (length: 30 m × inner diameter: 0.25 mm × film thickness: 0.25 µm). The hydrocarbon
yield (X) was calculated by GC-FID using Eq. 2.
𝑋 =∑ 𝑛𝑜+∑ 𝑛𝑖
∑ 𝑛𝑧× 100% (Eq. 2)
where, no = peak area of alkanes, ni= peak area of alkenes, nz= peak area of the total products. The selectivity
of the hydrocarbon products was determined by Eq. 3.
𝑆 =𝐶𝑖
∑ 𝑛𝑧× 100% (Eq.3)
where, ci= peak area of desired hydrocarbon, nz= peak area of total hydrocarbon.
The functional group of deoxygenated liquid products were identified using FTIR spectrometer (Perkin
Elmer (PC) Spectrum 100). The spectra were recorded within IR range of 500-4000 cm-1 and the resolution
was 4 cm-1.
3. Results and Discussion
3.1 Characterization of catalysts
XRD analysis
XRD analysis in Fig 1a-b showed the low and wide angles diffraction pattern of the catalysts. Kaolin showed
the presence of kaolinite phase with high intensity peaks appeared at 2θ = 12.4°, 23.7°, 24.9° and 38.4°
(JCPDS No. 14-0164) (Fig. 1a). Significant changes on the diffraction pattern were observed following
23
hydrothermal synthesis, with both S-ZSM-5 and T-ZSM-5 showed the diffraction peaks corresponded to the
ZSM-5 at 2θ = 7.8°, 8.7°, 23.0°, 23.8° and 24.0° (JCPDS No. 44-0003). For Al-MCM-41, a broad diffraction
peak appeared at 2θ = 15-30° corresponded to the amorphous phase of Al-MCM-41 [59]. The low angle
XRD analysis (Fig. 1b) of Al-MCM-41 showed three diffraction peaks within 2θ = 2-6° corresponded to the
(100), (110) and (200) diffraction planes. The peaks confirmed the formation of highly ordered hexagonal
mesostructures of Al-MCM-41 [11,60]. S-ZSM-5 synthesized using silicalite as structure directing agent
showed a weak diffraction peak at 2θ=2.1o that corresponded to the (100) diffraction plane. The presence of
this peak implied the formation of a lower ordered mesostructure within the ZSM-5 framework [60]. When
T-ZSM-5 was synthesized using TPAOH, the peaks associated with the ordered mesostructure were
negligible. In general, the mesoporosity of ZSM-5 was enhanced when silicalite was used as seeding template
during the two-steps crystallization of kaolin. The mesoporosity of aluminosilicate was further enhanced
when the synthesis was carried out in the absence MFI as structure directing agent, however the framework
structure was transformed into Al-MCM-41.
Fig. 1a-b
3. FTIR analysis
FTIR analysis of kaolin showed the absorption bands at 538 cm-1, 789 cm-1 and 914 cm-1 that were
corresponded to the vibrations of Al-O and (Al-O)-H bonds in Al[O(OH)]6 (Fig. 2a). Kaolin also showed
absorption bands at 430, 470, 752, 795, 1032 and 1114 cm-1, which were assigned to the Si-O bonds from
SiO4. The absence of absorption band associated with kaolin on S-ZSM-5, T-ZSM-5 and Al-MCM-41
indicated the phase transformation of kaolinite to silica-based materials framework. All the catalysts derived
from kaolin showed the characteristics absorption of zeolite framework at 450 cm-1 due to the vibration of
T-O-T (T is Al or Si atom). The catalysts also showed the adsorption bands at 795 and 1225 cm-1 assigned
to the internal and the external asymmetric stretching, respectively; and the band at 1100 cm-1 ascribed to
internal asymmetric stretching mode of T-O-T (between TO4 tetrahedral) [61]. S-ZSM-5 and T-ZSM-5
catalysts showed the formation of 550 cm-1 band which was the characteristic of MFI structure [62].
Meanwhile the absence of 550 cm-1 band on Al-MCM-41 further confirmed the formation of Al-MCM-41
framework [63]. The vibrational peak appeared at 960 cm-1 from Al-MCM-41 corresponded to Si-O
stretching vibration of Si-O-H group [64].
24
Fig. 2a-b
Surface acidity of the catalysts were analyzed using FTIR spectroscopy while employing pyridine as probe
molecule (Fig 2b). Pyridine was adsorbed onto the catalysts at room temperature and subsequently evacuated
at 150 ℃ and 300 ℃ in order to provide information on the acidity strength and the number of Brønsted (B)
and Lewis (L) sites. The absorption band appeared at 1450 cm-1 was corresponded to the Brønsted acidity,
meanwhile the band at 1540 cm-1 was assigned to the Lewis acidity [65]. The adsorption band observed at
1488 cm−1 was originated from adsorbed pyridine on both types of acidity [52]. Table 1 summarized the
calculated acidity of aluminosilicate catalysts. Al-MCM-41 showed the highest number of Lewis acid at
0.296 mmol/g followed by T-ZSM-5 at 0.284 mmol/g and S-ZSM-5 at 0.158 mmol/g. The number of Lewis
and Brønsted acid sites were reduced following evacuation at 300 ℃, which implied the presence of both
weak and medium strength acidity on the catalysts. T-ZSM-5 showed a higher Brønsted sites at 0.108
mmol/g followed by S-ZSM-5 at 0.072 mmol/g and Al-MCM-41 at 0.054 mmol/g. ZSM-5 produced from
TPAOH and silicalite seed showed a different concentration of acid sites despite similar initial Si/Al ratios.
The results implied the influence of organic template TPAOH for the formation of surface acidity in ZSM-
5. TPA+ was reported to facilitate the formation of zeolite-like aluminium sites via the arrangement of tiny
aluminosilicate clusters with tetrahedrally coordinated aluminium, which in return significantly enhanced
the acidity of ZSM-5 [66,67].
Table 1
N2 adsorption-desorption analysis
The textural properties of the catalysts were analyzed using nitrogen adsorption-desorption method (Fig. 3a
and Table 2). N2 adsorption analysis also provided evidences on the presence of both microporous and
mesoporous characteristics of hierarchical zeolite. All the catalysts exhibited different type of isotherms.
However, at low relative pressure (P/P0<0.1), all the catalysts showed significant increase of N2 adsorption
that was due to the presence of micropores. Similar trend was also observed at high relative pressure
(0.9<P/P0<1), due to the multilayer adsorption and capillary condensation of N2. For Al-MCM-41, a sharp
increase of N2 uptake at P/P0= 0.3-0.4 was observed as the typical characteristic of Al-MCM-41
mesoporosity. Al-MCM-41 also exhibited the largest surface area of 739 m2/g with the total pore volume of
0.85 cc/g. Al-MCM-41 also showed narrow distribution of mesopores with a very intense N2 adsorption
25
volume centered at 3.8 nm due to the formation of intra-particle mesopores [50] (Fig. 3b). T-ZSM-5
synthesized using TPAOH exhibited type I isotherm corresponded to the microporous zeolite. The pore size
was also measured at ~ 4.5-6.0 nm, however the mesopores were originated from inter-particles interaction.
S-ZSM-5 produced using silicalite showed the combination of type I and type IV isotherms suggesting the
formation of hierarchical structures of ZSM-5. The presence of intra-particle mesopores in S-ZSM-5 was
confirmed by the increased of N2 adsorption at P/P0= 0.3-0.4. However, the N2 volume was significantly
lower than Al-MCM-41. The surface area of T-ZSM-5 was determined at 220 m2/g with the total pore volume
was measured at 0.37 cc/g. When ZSM-5 was synthesized using silicalite as a seed, the surface area of S-
ZSM-5 was significantly enhanced to 439 m2/g and the total pore volume increased to 0.52 cc/g.
Fig. 3a-b
Table 2
Morphology analysis using SEM and TEM
SEM analysis provided information on the morphology of the catalysts synthesized using different types of
structure directing agent. S-ZSM-5 (Fig 4a) showed the formation of agglomerated particles that were
dominated by the prismatic structures with the particle size of 0.86-1.09 µm. Meanwhile, T-ZSM-5 catalyst
(Fig. 4b) showed the formation of cubic-shaped structure with the particle size of 0.90-1.04 µm. The
synthesis of porous Al-MCM-41 in the absence of structure directing agent showed the formation of non-
uniform crystallite structures with the average particle size of 0.50-1.05 µm (Fig. 4c).
Fig. 4a-c
HR-TEM analysis of S-ZSM-5 (Fig 5a) revealed the formation of hexagonal crystallite structures with
corrugated surfaces in agreement with the SEM analysis. The presence of well-ordered parallel mesopores
channel was observed with the pore diameters were estimated at 3.32 nm (Fig 5b). TEM analysis of T-ZSM-
5 showed the formation of cubical crystalline structure with the size was determined at ~ 400 nm (Fig 5c).
The presence of mesoporous channel in T-ZSM-5 was less evident in comparison to the S-ZSM-5, which
confirmed the results from N2 adsorption-desorption and low angle XRD (Fig. 5d). TEM analysis of Al-
MCM-41 exhibited the formation of intra-particulate one dimensional mesopores with the average pore size
of 3.49 nm (Fig 5e-f). The formation of parallel mesopore channel was more pronounced in Al-MCM-41
that indicated the highly-ordered mesopore channel was developed during the synthesis without the use of
26
MFI structure directing agent. The presence of CTABr as mesopore template controlled the growth of
parallel mesopores in Al-MCM-41.
Fig. 5a-f
29Si MAS NMR analysis
29Si MAS NMR analysis provided information of the silica environment in aluminosilicate at molecular level.
29Si MAS NMR spectra of S-ZSM-5 showed three deconvoluted peaks centered at -86, -97 and -110 ppm
(Fig 6a). The signal appeared at -110 and -97 ppm were corresponded to the Q4 linkage of Si(SiO)4 [68] and
Si(OSi)3OAl sites, respectively [69,70]. In T-ZSM-5, these peaks were slightly shifted to -111 and -101 ppm
presumably due to the high crystallinity of T-ZSM-5 compared to S-ZSM-5 [71]. S-ZSM-5 showed the
presence of weak resonance peak at -86 ppm, which was corresponded to the Q3 Si(OSi)3(OH) sites from the
amorphous phase of ZSM-5. The 29Si MAS NMR signal for Al-MCM-41 appeared at chemical shift of -83
and -89 ppm which were assigned to Q3 Si(OSi)3(OH) and Q4 Si(OSi)3OAl sites, respectively. The presence
of Q3 resonances implied the partial transformation of Si(SiO)3OAl to Si(SiO)3(OH). Al-MCM-41 also
showed a broad resonance peak due to the overlapping of multiple peaks at chemical shift of -97 and -108
ppm corresponded to the silicon sites Q4 Si(OSi)4 unit. The elemental composition of Si and Al determined
from 29Si MAS NMR deconvoluted data (Table 3) showed the Si/Al ratios of the catalysts were determined
at ~22 – 26.
Fig. 6a-c
Table 3
3.2 Catalytic deoxygenation of JCO
Deoxygenation of JCO was carried out at 350 ℃ for 1 h under N2 flow using S-ZSM-5, T-ZSM-5 and Al-
MCM-41 (Table 4). Al-MCM-41 showed high oil conversion at 20.04%, which was significantly higher
than T-ZSM-5 at 9.97% and S-ZSM-5 at 6.73%. Analysis of the liquid products from S-ZSM-5 revealed the
selectivity of hydrocarbon at 45.94% and oxygenates compound at 48.16%. Oxygenates were consisted of
carboxylic acid, aldehyde and ether compounds. Cycloalkane was also observed at 3.25% selectivity. The
selectivity of hydrocarbon was increased to 65.78% when using T-ZSM-5 with significant reduction of
oxygenates compound to 26.37%. When Al-MCM-41 was used as catalyst, hydrocarbons was produced at
83.68% of selectivity, and the formation oxygenates was significantly reduced to 4.77%. It is interesting to
27
note that increasing the mesoporosity of ZSM-5 when using silicalite as template was detrimental towards
deoxygenation reaction evident by the low conversion of oil at 6.73%. S-ZSM-5 also exhibited low
concentration of acidity in comparison to T-ZSM-5 and Al-MCM-41. The results suggested that the
deoxygenation of JCO is an acid catalyzed reaction and therefore the number of acid sites significantly
enhanced the conversion of oil to hydrocarbon.
Table 4.
Analysis of JCO composition showed the presence of 70% of unsaturated fatty acid which was consisted of
a mixture of oleic acid (C18:1) and linoleic acid (C18:2); with another 20% was saturated fatty palmitic acid
(C16:0) [10]. Therefore, detail analysis of the hydrocarbon resulted from the reaction provided insight into
the pathway of deoxygenation reaction. Fig 7 showed the distribution of hydrocarbon based on the number
of carbon chain, in which Al-MCM-41 showed high selectivity towards n-C15+n-C17 hydrocarbons.
Deoxygenation produced oxygen-free hydrocarbons with one atom carbon shorter than the parent fatty acid.
The formation of n-C15+n-C17 hydrocarbons indicated that the JCO oil underwent deoxygenation reaction
when using Al-MCM-41. The formation of light hydrocarbons fraction (C8-C14) were observed on S-ZSM-
5 and T-ZSM-5 catalysts that reduced the selectivity of deCOx products (n-C15+n-C17 hydrocarbons). Light
hydrocarbon was produced presumably due to the secondary hydrocracking reaction of the resulting
hydrocarbons or the fatty acids in JCO.
Fig. 7
3.2 Effect of reaction time on deoxygenation of JCO over Al-MCM-41
The effect of reaction time on the conversion and the selectivity of hydrocarbon was investigated using Al-
MCM-41 catalysts. The conversion was increased from 20% to 45% in 4h (Fig 8a). The composition of
hydrocarbon was further divided into n-C11-18 which was within the diesel hydrocarbon range, and n-C8-10 for
gasoline range (Fig. 8b). n-C11-18 hydrocarbon n was dominated the product throughout the reaction at ~
90% of selectivity. The appearance of n-C8-10 fraction was corresponded to the competing hydrocracking
reaction of JCO or the resulted hydrocarbon with acid sites on the catalysts [72].
Fig. 8a-b
JCO and liquid product from deoxygenated reaction were further characterised using FTIR analysis in order
to provide insight into the mechanistic steps of the reaction (Fig. 9a). The FTIR spectra of JCO showed the
28
presence of –CH stretching of the aliphatic chain absorption band at 2925 cm-1, the –C=O stretching of ester
at 1735 cm-1, the C-O-C stretching at 1161 cm-1, the –CH alkane and the =CH alkene bending vibrations at
1453 and 717 cm-1 respectively. The absorption band of –C=O (ester) and C-O-C (carbonyl) stretching were
the characteristics of oxygenates species in triglycerides that were used to evaluate the progress of
deoxygenation reaction [20]. The stretching vibration of –C=O in liquid product was slightly shifted from
1735 cm-1 (ester group) to 1700 cm-1 (carboxylic acid group) after 1h of reaction, indicated the dissociation
of ester bond to form intermediates fatty acid [73]. The observation was also supported by the elimination
of C-O-C band of the carbonyl group in JCO evident by the disappearance of the absorption band at 1161
cm-1 [74]. FTIR analysis indicated that the first step of reaction involved the transformation of triglycerides
to fatty acids that occurred on acid catalysts. As the reaction time increased to 4 h, the reduction of–C=O
peak intensity was observed which confirmed the elimination of carboxylate fragments of the free fatty acids.
It is also interesting to see that the C-O adsorption band was disappeared within the first 1h of the reaction,
meanwhile the C=O band only showed significant reduction after 4h of reaction. Considering the
deoxygenation involved removal of OCO group, we believe the differences of the intensity of the C-O and
C=O absorption bands provided crucial information on the mechanism of the reaction that will be discussed
in section 3.5.
Fig. 9a-b
3.4 Reusability and stability Al-MCM-41 catalyst
The stability Al-MCM-41 were evaluated based on the reusability of the catalyst and the formation of coke
deposits. The catalyst was filtered of 2h of reaction and reactivated by washing with hexane until the filtration
become colourless. The reactivated catalyst was subsequently used under similar reaction condition for five
times. Fig. 10 showed the conversion and the selectivity hydrocarbon that indicated the Al-MCM-41 catalyst
was active up to five reaction cycles with consistent hydrocarbon selectivity ~91%. However, hydrocarbon
selectivity reduced after 5th cycle at 80%, and therefore the catalyst was further characterized using TGA and
XRD analysis to provide information on the cause of deactivation (Fig. 11a-c). TGA-DTG-DSC analysis
showed the presence of 28% of coke on the catalysts that may have blocked the active sites of the reaction
[75]. TGA-DTG-DSC analysis also indicated the decomposition of carbon to CO2 at 300-500 ℃ in which
suggested the coke was consisted of a mixture of soft and hard carbon. Coke can be classified into
29
soft/thermal coke deposit which decomposed at temperature below 400 ℃, and hard/catalytic coke that
decomposed at temperature above 400 ℃ [14,76,77]. XRD analysis of the used catalysts showed the
hexagonal porous characteristic peak at 2θ= 2.3o (100) was slightly reduced (Fig. 11c) that suggested the
coke deposited within the hexagonal pores array of Al-MCM-41 framework and reduced the diffusion of
molecules reactant [78].
Fig. 10
Fig. 11a-c
3.5 Discussion
Selective deoxygenation of JCO under inert condition eliminated the carboxylate fragments of fatty acid via
decarboxylation and/or decarbonylation pathways. JCO was consisted of 20 % of free fatty acid and 70% of
triglycerides. In the presence of acid catalysts, triglycerides was hydrolysed to form palmitic acid, oleic acid,
stearic acid and linoleic acid (C16 and C18 fatty acids) [14]. The resulting fatty acids were further
deoxygenated to form n-C15 and n-C17 hydrocarbons. The presence of strong acid sites was important due to
the deoxygenation reaction was carried out at high temperatures ~350 oC. Pyridine adsorption analysis
showed that Al-MCM-41 has high number of Lewis acid sites in comparison to the ZSM-5. S-ZSM-5 showed
approximately 43% reduction of Lewis acidity at temperature above 300 oC meanwhile Al-MCM-41 only
showed 20 % reduction of Lewis acidity. Although the mesoporosity of S-ZSM-5 was significantly improved
when using silicate as template, the deficiency of high strength Lewis acid sites significantly reduced the
conversion of oil into hydrocarbons.
Analysis of the hydrocarbons composition from Al-MCM-41 and ZSM-5 indicated that the deoxygenation
reaction of JCO was in competition with hydrocracking reaction. Deoxygenation eliminated carbonyl group
in the fatty acid in order to form hydrocarbon with one atom carbon shorter than the parent structures (C15
and C17 hydrocarbons). Both deoxygenation and hydrocracking reactions required an acid catalyst to
dissociate the C-C bond for high conversion of oil to hydrocarbon. Cracking reaction of hydrocarbon
generally required a strong acid catalyst with high concentration of Brønsted acidity [31,79], meanwhile
deoxygenation occurred predominantly on Lewis acidity [72]. The ratio between Lewis to Brønsted acidity
indicated that Al-MCM-41 have a high number of Lewis acidity than the S-ZSM-5 and T-ZSM-5. However,
the porosity of catalysts also affected the conversion towards deoxygenation reaction. High selectivity
30
towards short-chain hydrocarbons fraction (C8-10) were observed when using S-ZSM-5 and T-ZSM-5. The
result indicated the reaction underwent secondary cracking pathway on S-ZSM-5 and T-ZSM-5. Catalytic
cracking into short-chain hydrocarbon can occur on the fatty acids, or the resulting hydrocarbons from
deoxygenation reaction, which consequently reduced the selectivity of hydrocarbon within the green diesel
composition (C11-18). The confined spaces of the zigzag pore structure and the narrow channel intersection
of ZSM-5 restricted the diffusion of molecular substrate, hence prolonged the interaction between acid sites
and hydrocarbon for secondary cracking reaction. Al-MCM-41 catalyzed deoxygenation reaction of JCO to
favor high production of nC15+17 hydrocarbon and simultaneously suppressed the formation of light chained
hydrocarbon from secondary hydrocracking reaction. Efficient diffusion of hydrocarbons prevented further
cracking reaction to light chained hydrocarbon. The narrow diameter of ZSM-5 pores that was generally
consisted of a zigzag and a straight channel connected via a narrow intersection restricted the diffusion of
fatty acids into the pores and therefore it can be suggested that catalytic cracking reaction may utilized acid
sites on the surface of the catalyst.
Fig. 12 illustrated the proposed mechanism of deoxygenation reaction of JCO over Al-MCM-41 catalyst.
Deoxygenation of JCO occurred via decarboxylation of fatty acid evident by the production of CO2 gas.
Analysis of the gas product from deoxygenation of JCO using GC-TCD (Fig 9b) indicated the domination
of CO2 with 100% selectivity within 1h of reaction. Increasing the reaction time significantly reduced the
selectivity of CO2 but enhanced the formation of CO suggested that fatty acids underwent decarbonylation
reaction to release CO. Traces amount of CH4 was also observed presumably due to the methanation reaction
between CO and CO2 gas under the presence of H2. Since the reaction was carried out in the absence of H2,
there is a possibility that H2 was produced from the catalytic cracking reaction.
Fig. 12
4. Conclusions
Kaolin was transformed into highly selective Al-MCM-41 catalysts for deoxygenation of Jatropha Curcas
oil into green diesel. Al-MCM-41 activity was compared with microporous ZSM-5 and hierarchical ZSM-5
in order to elucidate the effect of porosity towards the formation of green diesel hydrocarbon. High
conversion and selectivity towards deoxygenation reaction was observed on Al-MCM-41 meanwhile ZSM-
5 showed the competition between deoxygenation and catalytic hydrocracking reaction. Lewis acidity was
31
responsible for high conversion of JCO. Highly ordered mesoporous Al-MCM-41 with one-dimensional
hexagonal pore arrays facilitated the diffusion of deoxygenated products that prevented the secondary
cracking reaction, consequently enhanced the n-C15+n-C17 hydrocarbon yield. Al-MCM-41 also displayed
high stability and reusability up to five cycles with consistent hydrocarbon selectivity.
Acknowledgement
The authors would like to acknowledge The Ministry of Research, Technology and Higher Educaction of
Republic Indonesia under PMDSU scholarship with contract number 1290/PKS/ITS/2020 and local ITS
grant no. 836/PKS/ITS/2020 for funding the research.
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Table 1. Number of Brønsted and Lewis acid sites of the catalysts from pyridine adsorption
Sample
Number of acid site (mmol/g)
B/L L/B Brønsted Lewis B+L
S-ZSM-5 (150 0C) 0.072 0.158 0.230 0.455 2.194
S-ZSM-5 (300 0C) 0.038 0.089 0.127 0.426 2.342
T-ZSM-5 (150 0C) 0.108 0.284 0.392 0.380 2.629
T-ZSM-5 (300 0C) 0.073 0.198 0.271 0.369 2.712
Al-MCM-41 (150 0C) 0.054 0.296 0.350 0.182 5.481
Al-MCM-41 (300 0C) 0.014 0.234 0.248 0.059 16.710
Table 2. Physicochemical properties of all samples
No Template
SBET
(m2/g)a
Surface
area
(m2/g)
Pore volume (cc/g)
Dmeso (nm) d Product
e
Smeso
Smic
c Vmesob Vmic
c Vtotal
1 Silicalite+
CTABr 439 149 289 0.38 0.14 0.52 3.6; 5.6 ZSM-5
2 TPAOH
+CTABr 220 118 102 0.34 0.03 0.37 5.1 ZSM-5
3 CTABr 739 260 478 0.56 0.29 0.85 3.8
Al-
MCM-
41
a SBET (Total surface area) by BET method.
b Vmeso by DFT method
c Smicro and Vmicro (micropore volume) by t-plot method
d Dmeso by DFT method
37
e Product by XRD technique
Table 3. Chemical shifts and Si/Al ratio from 29Si NMR
Samples
Chemical shift (ppm) and area (%) deconvoluted peak
Si/Al Q4 (4Si, 0Al) Q4 (4Si, 0Al) Q4 (3Si, 1Al) Q3 (3Si, 1OH)
S-ZSM-5 -110 (84.87)
- -97 (13.09) -86 (2.04) 26.44
T-ZSM-5
-111 (83.65)
-
-101 (16.35) - 24.46
Al-MCM-41 -108 (42.86) -97 (28.95) -89 (14.92) -83 (13.27) 22.61
Table 4. Conversion and selectivity of liquid products from catalytic deoxygenation of JCO
Catalysts Xoils, %
Selectivity
Hydrocarbon, %
Selectivity
Cycloalkane,
%
Oxygenates compound, %
S-ZSM-5 6.73 45.94 3.25 48.19
T-ZSM-5 9.97 65.78 6.35 26.37
Al-MCM-41 20.04 83.68 11.52 4.77
38
Fig 1. (a) Wide angle and (b) low angle XRD analysis of kaolin, Al-MCM-41, ZSM-5
synthesized using TPAOH (T-ZSM-5) and hierarchical ZSM-5 synthesized using silicate (S-
ZSM-5).
Fig 2. FTIR framework (a) and pyridine adsorption (b) spectra of kaolin, Al-MCM-41, ZSM-5
synthesized using TPAOH (T-ZSM-5) and hierarchical ZSM-5 synthesized using silicate (S-
ZSM-5).
39
Fig 3a. N2 adsorption-desorption isotherm; b. pore size distribution by DFT method of Al-
MCM-41, ZSM-5 synthesized using TPAOH (T-ZSM-5) and hierarchical ZSM-5 synthesized
using silicate (S-ZSM-5).
40
Fig 4. SEM images of the S-ZSM-5 (a), T-ZSM-5 (b) and Al-MCM-41 (c)
41
Fig 5. TEM images of the S-ZSM-5 (a,b), T-ZSM-5 (c,d) and Al-MCM-41 (e,f)
42
4. Fig 6. 29Si NMR deconvoluted spectra of S-ZSM-5 (a), T-ZSM-5 (b) and Al-MCM-41 (c)
43
Fig 7. Hydrocarbon distribution from catalytic deoxygenation reaction of JCO on Al-MCM-41,
ZSM-5 synthesized using TPAOH (T-ZSM-5) and hierarchical ZSM-5 synthesized using
silicate (S-ZSM-5).
Fig 8a. Conversion of JCO and b. Selectivity of hydrocarbon on Al-MCM-41 catalyst as a
function of time. Hydrocarbon composition was divided into gasoline fractions (C8-10) and
diesel fraction (C11-18)
44
Fig 9a. FTIR spectra of JCO and liquid deoxygenated products over 4h of reaction, and b. Gas
products analyzed from JCO reaction.
Fig 10. Reusability investigation of JCO deoxygenation reaction over Al-MCM-41 using 3
wt.% catalyst loading at 350 ℃ within 2 h under inert atmosphere. (a) Conversion of JCO, and
(b) selectivity of hydrocarbon from liquid product
45
Fig 11. TG-DTG-DSC profile of fresh (a) and spent catalyst (b) and low angle XRD pattern of
fresh and spent catalyst (c)
Fig 12. Reaction pathway of JCO deoxygenation
46
LAMPIRAN 1 Tabel Daftar Luaran
Program : H-IMPACT - PENELITIAN HIGH IMPACT
Nama Ketua Tim : Prof. Dr. Didik Prasetyoko
Judul : Bio-Jetfuels Range Alkanes Production from Kemiri Sunan
Oil (Reutalis Trisperma Oil) via Hydro/-Deoxygenation
Reaction by Metal/Mesoporous Aluminosilicates from local
sources
1.Artikel Jurnal
No Judul Artikel Nama Jurnal Status Kemajuan*)
1. Solvent-free selective
deoxygenation of Jatropha Curcas
oil to green diesel on Al-MCM-41
from kaolin with suppressed
hydrocracking activity
Journal of The Energy
Institute
Draft
*) Status kemajuan: Persiapan, submitted, under review, accepted, published
2. Artikel Konferensi
No Judul Artikel Nama Konferensi (Nama
Penyelenggara, Tempat,
Tanggal)
Status Kemajuan*)
1 Biojetfuel Production From
Reutealis Trisperm Oil Over
Indonesian Red Mud Based
Catalyst
ICCME 2020, Undip
Semarang, 6-7 Oktober
2020
Terdaftar
*) Status kemajuan: Persiapan, submitted, under review, accepted, presented
3. Paten
No Judul Usulan Paten Status Kemajuan
*) Status kemajuan: Persiapan, submitted, under review
4. Buku
No Judul Buku (Rencana) Penerbit Status Kemajuan*)
*) Status kemajuan: Persiapan, under review, published
5. Hasil Lain
No Nama Output Detail Output Status Kemajuan*)
47
*) Status kemajuan: cantumkan status kemajuan sesuai kondisi saat ini
6. Disertasi/Tesis/Tugas Akhir/PKM yang dihasilkan
No Nama Mahasiswa NRP Judul Status*)
*) Status kemajuan: cantumkan lulus dan tahun kelulusan atau in progress