pubs.acs.

org/IECR Article

Enhancing Brønsted and Lewis Acid Sites of the Utilized Spent RFCC
Catalyst Waste for the Continuous Cracking Process of Palm Oil to
Biofuels
I. Istadi,* Teguh Riyanto, Luqman Buchori, Didi Dwi Anggoro, G. Gilbert, Kania Adelia Meiranti,
and Elok Khofiyanida
Cite This: Ind. Eng. Chem. Res. 2020, 59, 9459−9468 Read Online
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sı Supporting Information

ABSTRACT: Catalyst waste from the residue fluid catalytic

cracking (RFCC) plant process can still be utilized to catalyze the
catalytic cracking of palm oil to fuels. However, we should
Downloaded via Istadi Istadi on May 21, 2020 at 04:07:26 (UTC).

regenerate the active sites of the catalyst waste. This paper focuses
on enhancement of Brønsted and Lewis acid sites on the spent
RFCC catalyst waste through various acid treatments in order to
regenerate its catalyst active sites. In order to regenerate the
Brønsted and the Lewis acid sites as active sites in the palm oil
catalytic cracking, the spent RFCC catalyst was treated by citric
acid, sulfuric acid, and mixture of both acids. The catalysts were
characterized by X-ray fluorescence, X-ray diffraction, Brunauer−
Emmett−Teller-Barrett−Joyner−Halenda, and pyridine-FTIR
analysis. The modified catalyst performance was tested over a fixed bed reactor for the catalytic cracking process of palm oil to
liquid fuels. It was found that the acid treatment on the spent RFCC catalyst can increase surface area, pore volume, and Brønsted to
Lewis acid site ratio of catalysts. The Brønsted acid sites of the spent RFCC catalyst strongly increase by the treatment using sulfuric
acid, which is because of the proton transfer from acid to catalyst and because of the formation of sulfate groups (HOSO3−) in the
catalysts. It was found that the Brønsted acid site leads to the formation of long-chain hydrocarbon, while the Lewis acid site
pronounces the formation of short-chain hydrocarbon and coke. Moreover, the total acidity and the Lewis acid site amount on the
catalyst have roles in the formation of hydrocarbon fraction in the liquid product.

1. INTRODUCTION chain hydrocarbon, the relatively equal ratio of saturated and

Biofuel appears as a promising alternative as a renewable
energy because of the increase in energy demand and the
decrease in fossil fuel reserves. Biofuels, such as biodiesel
(FAME, fatty acid methyl ester), green gasoline (bio-gasoline),
green kerosene, and green diesel (fossil diesel-like), can be
produced from vegetable oils. Biodiesel production from
vegetable oils was widely studied by researchers, in which
the most developed process of biodiesel production was
transesterification.1−3 However, biodiesel needs to be mixed
with fossil diesel, and its hygroscopicity caused the clogging in
the engine filter.4 Furthermore, the engine needs to be
modified for the use in mixtures with fossil diesel at levels
above 20%.4 The other processes for biofuel (bio-gasoline,
green kerosene, and green diesel) production are thermal
cracking,5 catalytic cracking,6−8 and hydrodeoxygenation9 and
deoxygenation10−12 reaction. The catalytic cracking was widely
developed by researchers because of low energy requirement,
low operational cost, and high flexibility to utilize many
vegetable oil types rather than thermal cracking.13 Palm oil is
the most favorable vegetable oil as the feedstock for biofuel
production,14,15 which is because of the high content of long-
unsaturated oil content,16 giving significant contribution on
aromatic compounds in the liquid product,5 and abundant
availability in the world especially in Indonesia and Malaysia
regions.
The catalytic cracking reaction of palm oil follows the chain
reaction mechanism involving initiation, propagation, and
termination.17 The main step is the initiation step, which is the
attack of one Brønsted acid site or Lewis acid site from the
catalyst to the reactant molecule to form a carbenium ion as a
carbocation.17 However, until now, the role of each acid site
(Brønsted or Lewis acid site) was still not clear, although many
researchers suggested in this case. For this reason, many
researchers have developed the heterogeneous acid catalysts
Received: March 3, 2020
Revised: April 26, 2020
Accepted: April 29, 2020
Published: April 29, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c01061

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Industrial & Engineering Chemistry Research
containing the high Brønsted acid site and/or Lewis acid site
to promote the cracking process by enhancing the number of
catalyst acid sites. Previously, the enhancement of the catalyst
acid sites could be carried out by metal atom modification18−20
and treatment using acid chemicals.21−24 They reported that
the modification of the catalysts acidity using metal
impregnation on Y zeolite could increase the Lewis acid site
amount because of the presence of unpaired electrons in the
metals.20 However, the metal impregnation could decrease the
Brønsted acid site present in the catalysts because of the ion
exchange of acidic proton with metals during the impregnation
process.19 Thus, the metal modification of zeolite-based
catalyst seems not interesting because of the generation of
the Lewis acid site amount only.
The acid treatment of Hβ-zeolite using citric acid could
increase the amount of strong and weak acids, but the acid
strength decreased.21 Interestingly, the citric acid treatment of
the zeolite beta has role of both dealumination at Si(2Al) sites
and realumination at Si(0Al) sites.21 The dealumination
process is expected to increase the Lewis acid site, as reported
that the amount of the Lewis acid site could be increased by
the raising Si/Al ratio.25 Another study reported that the
amount of total Brønsted acid sites of zeolite increased, when
the catalyst was treated for 5 min with 0.2 M HF/NH4F.24 The
significant decrease of the total Lewis sites is because of the
partial reinsertion in the framework of some of the extra-
framework aluminum. Meanwhile, the Brønsted acid site of
MCM-41 was strongly generated by treatment using sulfuric
acid because of generation of sulfate groups (HOSO3−) on the
catalyst.26
The catalyst waste of residue fluid catalytic cracking
(RFCC) could be potentially reused/reutilized for catalyzing
the cracking process of palm oil, which is abundantly available
in Indonesia, to produce liquid biofuels (gasoline, kerosene,
avtur, and/or diesel). In fact, the waste spent RFCC catalyst
has still lower cracking performance because of catalyst
deactivation during the industrial cracking process. The
catalyst deactivation is because of lowering of the acid active
sites and the coke pore blocking. According to previous
studies, the Brønsted/Lewis acid sites on the spent RFCC
catalyst can be regenerated by some special treatments, which
in turn, the catalyst can be reused as a good catalyst for
cracking palm oil to liquid fuels. There is no previous research
study which focused on the acid treatments of the spent RFCC
catalyst for enhancing the Brønsted and Lewis acid sites,
supporting the catalytic cracking of palm oil. Therefore, this
study investigated the enhancement of Brønsted and Lewis
acid sites on the spent RFCC catalyst waste through the
various acid treatments. The improvement of acid site amount
on the catalyst can increase the catalyst performance on the
cracking process of palm oil into biofuels by regenerating the
Brønsted/Lewis acid sites, increasing catalyst surface area, and
focusing on determination of the role of these acid sites
(whether having similar role like in cracking process of crude
oil or not).
2. MATERIALS AND METHODS
2.1. Materials of Research and Catalyst Preparation.
Materials used in this study were the spent RFCC catalyst
waste from a petroleum company, citric acid (99%, Merck),
and sulfuric acid (96%, Merck). The HY-zeolite catalyst was
obtained from Zeolyst International, which is commercially
denoted as CBV760. The raw material used in this cracking
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process was refined palm oil purchased from the local market.
Its composition based on GC−MS analysis is provided in
Table 1 (Figure S1 Supporting Information), in which palmitic
Table 1. Palm Oil Composition as the Raw Material by
GC−MS Analysis
molecular composition
components formula (%)
palmitic acid (C16:0) C16H32O2 43.30
oleic acid (C18:1) C18H34O2 18.51
2-monopalmitin C19H38O4 3.25
Z-13-octadecenyl acetate C20H38O2 2.03
oleic acid, 3-(oxtadecyloxy)propyl ester C39H76O3 1.47
1-nonadecene C19H38 16.27
11-hexacosyne C26H50 5.80
9-tricosene C23H46 5.68
2-pentadecanone C15H30O 1.34
(Z,Z)-3,9-cis-6,7-epoxy-nonadecadiene C19H34O 1.18
1-heptadecanol C17H36O 1.17
acid is the main component. The other components appear
because of the refining process to palm oil crude. In order to
flush the oxygen content in the tubing and reactor installation,
a nitrogen (99%) gas was flowed to the reactor installation.
The commercial HY-zeolite was dried in an electric oven
(Memmert) at 110 °C for 12 h. The dried HY-zeolite catalyst
was then calcined in a box furnace (NEY VULCAN 3-550) at
550 °C for 4 h and denoted as the HY catalyst. The spent
RFCC catalyst waste was washed using demineralized water
and dried in an electric oven (Memmert) at 110 °C for 12 h.
The dried spent RFCC catalyst was then calcined in a box
furnace (NEY VULCAN 3-550) at 550 °C for 4 h and denoted
as the RFCC catalyst. The acid treatment of the spent RFCC
catalyst was conducted using citric acid, sulfuric acid, or
combination of citric and sulfuric acids. Before the acid
treatment, the spent RFCC catalyst was washed using
demineralized water and dried in an electric oven (Memmert)
at 110 °C for 12 h. The spent RFCC catalyst then was soaked
in 3 M of acid solution at 80 °C for 30 min. The slurry was
then filtered and washed with demineralized water to remove
the excess acid. The sample was then dried for 24 h at 110 °C
in an electric oven (Memmert) and then calcined in a box
furnace (NEY VULCAN 3-550) at 550 °C for 4 h. The spent
RFCC catalyst was then denoted as: RFCC for without
treatment, RFCC-C for citric acid treatment, RFCC-S for
sulfuric acid treatment, and RFCC-M for mixture of citric and
sulfuric acid treatment.
2.2. Catalyst Characterization. The X-ray fluorescence
(XRF) analysis method (Rigaku Supermini 200 Benchtop
WDXRF Spectrometer) was used to determine the elemental
metal content. In order to determine the crystal structure,
catalysts were analyzed using the X-ray diffraction (XRD)
(Shimadzu 7000) method. The Cu Kα radiation (λ = 1.54 Å)
was operated at 30 mA and 30 kV. The diffraction patterns
were generated at 2θ angle ranges of 10−60° with a scanning
speed of 4° min−1. The catalyst surface area was determined
using the Brunauer−Emmett−Teller (BET) surface area
method while the pore volume and average pore size were
determined by the Barrett−Joyner−Halenda (BJH) method
(ChemBET PULSAR Quantachrome). Pyridine-probed Four-
ier Transform Infrared (pyridine-FTIR) spectroscopy was used
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to determine the presence and concentration of Brønsted and mOLP

Yield of OLP(%) = × 100
Lewis acid sites on the catalysts. mfeed (3)
2.3. Catalyst Performance Testing. The treated spent
RFCC catalysts were tested for catalytic cracking reaction of mgas
Yield of gas(%) = × 100
palm oil over a continuous fixed bed reactor (Figure 1) to mfeed (4)
mcoke
Yield of coke(%) = × 100
mfeed (5)
mgasoline(C5 − C12)
Selectivityof gasoline(%) = × 100
mfeed − munreactedpalmoil
(6)
mkerosene(C13 − C14)
Selectivityof kerosene(%) = × 100
mfeed − munreactedpalmoil
(7)
mdiesel(C15 − C18)
Selectivityof diesel (%) = × 100
mfeed − munreactedpalmoil
Figure 1. Catalytic conventional reactor used for catalytic conversion (8)
of palm oil to biofuels: (1) palm oil tank, (2) peristaltic pump, (3) where mfeed is equal to the mass of palm oil fed to the reactor,
nitrogen gas tank (N2), (4) flowmeter−rotameter, (5) electric mgas is the mass of gas product, mcoke is the mass of coke, molp is
preheater, (6) thermocouple, (7) fixed-bed reactor, (8) electric the mass of OLP, and munreacted palm oil is the mass of unreacted
heater, (9) catalyst bed, (10) glass wool, (11) chiller, (12) condenser, palm oil.
and (13) product collector.
3. RESULTS AND DISCUSSION
produce liquid fuels. From Figure 1, the stainless steel tube was 3.1. Catalyst Characterization. 3.1.1. XRF Analysis.
used as a fixed bed reactor with an inside diameter of 1 in. The Metal content in acid-treated spent RFCC catalysts was
reactor was placed within a heated zone of electrical heater. elementally identified using XRF analysis (Table 2). From
The reactor temperature was measured and controlled using a
digital temperature controller. The catalyst (5 g) was put inside Table 2. XRF Analysis of Spent RFCC and Acid-Treated
the fixed bed reactor, which was supported by the glass wool. Spent RFCC Catalysts
In order to eliminate the oxygen content within all tubing and
metal composition of catalysts (% wt)
reactor, the reactor−tubing installation was flushed by nitrogen
gas flow for 15 min at 100 cm3/min. The reactor was then component HY RFCC RFCC-C RFCC-S RFCC-M
heated up to 450 °C. The palm oil, as the raw material, was fed Si 14.582 10.290 7.974 5.858 9.554
into the reactor at a weight hourly space velocity (WHSV) of Al 0.343 3.383 6.140 3.479 2.520
0.365 min−1. The vapor product of bottom section of the Ni 2.165 1.167 0.828 2.309
reactor was condensed into the liquid product using a Ti 0.462 0.320 0.227 0.637
condenser. The liquid product was then collected in a flask S 0.005 0.076 0.040 1.853 1.098
and was analyzed using gas chromatography−mass spectrom- Fe 0.009 0.685 0.297 0.179 0.503
etry (GC−MS). The liquid product was taken at the first 2 h P 0.010 0.142 0.041 0.042 0.064
after the steady state was achieved for GC−MS analysis La 1.146 0.179 0.390 0.501
purposes. Regarding this matter, an assumption was then taken Ce 0.599 0.153 0.199 0.350
that the steady-state condition was achieved after 30 min time K 0.014 0.171 0.095 0.049 0.139
on stream. Ca 0.013 0.128 0.054 0.052 0.108
The main products of this cracking process are gas, coke, V 0.074
and liquid biofuels or well-known as the organic liquid product Co 0.054 0.033 0.022 0.067
(OLP) for the cracking process of vegetable oils. Determi- Zn 0.014 0.006 0.006 0.011
nation of component identification and compositions of liquid Sr 0.011 0.006 0.005 0.009
biofuel product was conducted using GC−MS (QP2010S Y 0.006
SHIMADZU, DB-1 column). The samples were analyzed at 50 Zr 0.015 0.008 0.007 0.014
°C oven temperature (hold for 5 min) and ramped 10 °C· Nd 0.296 0.090
min−1 to 260 °C and held for 33 min. The results of detail Gd 0.112
GC−MS analysis are presented in the Supporting Information Si/Al ratio 42.476 3.042 1.299 1.684 3.792
(Table S1 and Figures S1 and S2). The conversion, yield, and
selectivity were calculated from the steady-state mass balance
using the following equations Table 2, the Si/Al ratios of acid-treated spent RFCC catalysts
are varied because of dealumination, desilication, or both of
mfeed = mgas + mcoke + mOLP + m unreactedpalmoil (1) these processes occurring simultaneously during the acid
mfeed − munreactedpalmoil treatment. However, the HY catalyst has the highest Si/Al
Conversion(%) = × 100 ratio. It is shown that the silica content of spent RFCC
mfeed (2) catalysts decreases during the acid treatment, which may be
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because of dissolution of silica, as suggested by Omegna et al.27
that the silica could dissolve during acid treatment of the
zeolite-based catalyst. It is also found that the acid treatment of
spent RFCC catalyst using citric acid decreases the silica to
aluminum ratio of catalyst (or increasing aluminum to silica
ratio). This phenomenon suggests that the citric acid treatment
leads to the reinsertion of Al into the catalyst, which controls
both dealumination and realumination. The dealumination
process is the removal of aluminum from zeolite frameworks
while realumination means the reinsertion of aluminum into
the frameworks. This finding agrees to previous research21 that
the citric acid treatment of zeolite beta has role of both
dealumination at Si(2Al) sites and realumination at Si(0Al)
sites. Fan et al.28 also reported that the citric acid treatment of
steamed HZSM-5 zeolite could support the realumination
process that was proved with the increase of the peak intensity,
and the concentration of tetrahedrally coordinated FAl at 54
ppm corresponds to 27Al MAS NMR analysis.
The spent RFCC catalyst contains many rare earth metals. It
may because of the design of catalyst or because of the catalyst
deactivation through metal poisoning.29 As reported by
Cerqueira et al.,29 the FCC feedstock may contain many
contaminant metals, depending on the crude oil sources. The
most common metals acting as the contaminants are iron,
nickel, vanadium, and sodium.30 As can be seen in Table 2, the
acid treatment affected the metal content in the catalyst. The
metal content of spent RFCC catalyst decreases, indicating
that leaching of metal occurred during the acid treatment.
Interestingly, the sulfur content increases during the sulfuric
acid treatment. It suggests that the treatment using sulfuric
acid provides the sulfur impregnation onto the catalyst surface.
However, both citric acid and sulfuric acid can leach the metal
and decrease the metal content in the spent RFCC catalyst, as
reported in Table 2. Cho et al.31 reported that the acid
treatment of spent RFCC catalyst could remove several metals.
The metal leaching from zeolite occurred through the
formation of complex molecule between the acid molecule
and metal.22,32 As the acid chemical can act as the ligand or
chelating agent, acid chemical can assist mineral dissolution by
adsorbing on mineral surfaces and forming highly soluble
complexes with metal ions.32 Even though the acid treatment
could leach the metal content of spent RFCC catalyst, the
mixed acid treatment could increase the silica to aluminum
ratio (Si/Al ratio). It suggested that the mixed acid (sulfuric
acid and citric acid) treatment leads to dealumination process,
besides desilication process. However, both silica and
aluminum decrease during the acid treatment.
3.1.2. XRD Analysis. XRD analysis was conducted to
determine the crystal structure of catalysts (Figure 2). It is
found that the XRD pattern of spent RFCC catalyst before
treatment and after treatment is not significantly different. The
acid treatments on the spent RFCC catalysts do not shift the
peaks significantly. The acid treatment on the spent RFCC
catalyst does not significantly change the crystal structure and
crystallinity of catalyst. Therefore, the various acid treatments
only affect the Si/Al ratio, but they do not impact significantly
on the crystal structure.
3.1.3. Surface Area and Pore Size Analysis. The surface
area and pore size/volume properties of the catalysts were
determined by BET and BJH methods, respectively. Table 3
provides the characterization results of surface area, pore
volume, and average pore size of the spent RFCC and acid-
treated spent RFCC catalysts. From Table 3, the surface area
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Figure 2. XRD pattern of the modified spent RFCC catalysts and
comparison to the commercial HY-zeolite catalyst.
Table 3. Surface Area, Pore Volume, and Average Pore of
Treated Spent RFCC Catalysts and Commercial HY-Zeolite
surface areaa pore volumeb average pore sizeb
catalysts (m2/g) (cm3/g) (nm)
HY 633.64
RFCC 107.66 0.021 1.91
RFCC-C 144.78 0.038 1.71
RFCC-S 75.37 0.052 1.53
RFCC-M 129.56 0.040 1.52
a
BET method. bBJH method.
of the spent RFCC catalyst increases after acid treatments,
except for the sulfuric acid-treated catalyst. However, the
commercial HY-zeolite catalyst has the highest surface area. An
exception appears on the RFCC-S catalyst, where the surface
area of the spent RFCC after sulfuric acid treatment decreases.
It is caused by the coalescence process during the calcination
process in the presence of acid, as suggested by Lee et al.33
They reported that the sulfate group had a great effect on
decreasing the surface area of silica−titania catalyst. Moreover,
the decrease of catalyst surface area after the sulfuric acid
treatment indicates that sulfate groups have been impregnated
on the pore of the spent RFCC catalyst, indicating decrease of
pore size. It agrees with the XRF analysis (Table 2), which
reports the presence and increasing of sulfur metal on the
catalyst. The decreasing catalyst surface area was also suggested
by Poh et al.,26 and that the sulfuric acid treatment on the
AlMCM-41 catalyst could decrease the surface area because of
the immobilization of sulfate groups in the pores of MCM-41.
Increasing surface area of the spent RFCC catalyst because
of citric acid or mixed acid treating is caused by the generation
of higher pore volume during the acid treatment. The pore size
distributions of spent RFCC catalysts from BJH analysis are
provided in Figure 3. It is clearly shown that the acid
treatments lead to the high pore volume, which is caused by
the surface cracks and void formation of the spent RFCC
catalyst.34 As reported in XRF analysis (Table 2), the acid
treatments could remove the metals in the spent RFCC
catalyst through metal leaching by acid. This process can lead
to the void formation in the spent RFCC catalyst, affecting
high pore volume formation. It was also reported in the XRF
analysis section (Table 2) that Si and Al atoms also could
dissolve during acid treatment. The dissolution of Si and Al
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Figure 3. Pore size distribution of nontreated spent RFCC and acid-
treated spent RFCC catalysts.
into acid solution can lead to the surface cracks and tailor the
void formation. These phenomena are supported by previous
finding that the acid treatment of zeolite catalyst led to the
formation of complex molecule between the acid molecule and
aluminum, which, in turn, causes widening of the catalyst
pores.22,35
3.1.4. Pyridine-Probed FTIR Analysis for Acidity Character-
ization. Acidity property of the acid-treated spent RFCC
catalysts was analyzed using FTIR analysis, using pyridine as a
probe molecule. This characterization method was conducted
to determine or to proof the presence of the Brønsted and/or
Lewis acid sites on the catalysts and to quantify the acid
amount/concentration. The Brønsted and Lewis acid sites can
be determined by the presence of the bands around 1545 and
1455 cm −1 using the pyridine-probed FTIR method,
respectively, as shown in Figure 4.22,36 However, peak areas
Figure 4. Infrared spectroscopy of the pyridine adsorption profile of
spent RFCC and acid-treated spent RFCC catalysts (LA: Lewis acid;
BA: Brønsted acid).
of the found Brønsted and Lewis acid sites were different for
each catalyst, which shows different amount or concentration
of both acid sites on the catalysts, as presented in Table 4. As
can be seen in Table 4, the acid (sulfuric acid and/or citric
acid) treatment affects the acid site amount/concentration of
the catalysts. Both acid site types can be regenerated or
degraded during the acid treatment, which depends on the acid
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Table 4. Identification and Amount/Concentration of
Brønsted and Lewis Acid Sites of HY-Zeolite and Acid-
Treated Spent RFCC Catalysts
Lewis acid total acid
site Brønsted acid site Brønsted/Lewis
catalysts (μmol/g) site (μmol/g) (μmol/g) ratio
HY 56.36 1.64 58.00 0.03
RFCC 70.22 54.01 124.23 0.77
RFCC-C 57.20 44.34 101.54 0.78
RFCC-S 60.27 228.21 288.48 3.79
RFCC-M 119.80 203.06 322.86 1.70
sources. However, the Brønsted to Lewis acid ratio increases
after the acid treatment (Table 4) because of the proton
transfer from acid to the catalysts during the acid treatment on
the spent RFCC catalyst. As the comparison to the commercial
catalyst, the commercial HY catalyst has the lowest value of the
Brønsted to Lewis acid ratio.
The citric acid treatment lowers the acid site amount/
concentration on the spent RFCC catalyst, but the reduction is
not significant. From Figure 4, the band around 1545 cm−1
decreases, which shows degradation of Brønsted acid site by
the citric acid treatment because of the decrease of (Si(OH)−
Al) groups, as reported by Vieira et al.22 They reported that
the citric acid treatment on HZSM-5 could decrease the
groups of (Si(OH)−Al), representing the presence of Brønsted
acid site. Interestingly, the amount of Brønsted acid site of the
spent RFCC catalyst, RFCC-S treated by sulfuric acid,
increases significantly because of the introduction of sulfate
groups (HOSO3−) into the catalyst, as also suggested by Poh
et al.26 These sulfate groups may form the bond with the
octahedral aluminum presence in the catalyst26 that can
increase the amount of Brønsted acid site on the catalysts.
Therefore, it is suggested that the Brønsted acid site generated
on the spent RFCC catalysts over sulfuric acid treatment is
contributed by the sulfate groups (HOSO3−) on the catalysts.
Moreover, it strongly suggests that the sulfuric acid treatment
has high positive effect on regeneration of Brønsted acid site of
the spent RFCC catalyst. A similar trend was reported that the
sulfuric acid-treated catalyst contains only Brønsted acid
sites.37 It was also reported by several researchers that the
treatment of mesopore alumina using sulfuric acid could
increase the Brønsted acid site amount.37,38
Meanwhile, the Lewis acid site amount of the catalysts seems
to be in line with the trend of Si/Al ratio. The higher the Si/Al
ratio, the higher the Lewis acid site amount. Based on the XRF
analysis (Table 2), the Si/Al ratio is different for each catalyst,
which is because of the acid leaching. It is also reported that
the amount of Lewis acid site increases with the Si/Al ratio.25
On the other hand, the mixed sulfuric acid and citric acid for
catalyst treatment (spent RFCC-M catalyst) has interesting
result in case of acid site generation. The mixed acid treatment
can regenerate both the Brønsted and Lewis acid sites
simultaneously. The Lewis and Brønsted acid sites are
regenerated because of the high Si/Al ratio, affecting the
defect site, and because of the proton transfer from sulfuric
acid to the catalyst and the formation of sulfate groups on the
catalyst, respectively (Figure 5).25 It is found that synergistic
roles of sulfuric acid and citric acid cause the generation of
both Brønsted and Lewis acid sites.
3.2. Catalyst Performance Testing on Catalytic
Cracking of Palm Oil. The catalyst performance was tested
on the palm oil cracking over a conventional continuous flow
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Figure 5. Brønsted and Lewis acid sites generated according to the Si
content.
packed bed reactor to produce liquid fuels (gasoline, kerosene,
avtur, and/or diesel ranges). Figure 6 presents triglyceride
Figure 6. Effect of catalyst type on the cracking product distribution.
conversion and product yield of palm oil catalytic cracking
using the different catalysts (HY, RFCC, RFCC-C, RFCC-S,
and RFCC-M). All catalysts can produce OLP or liquid fuels,
as the most dominant component produced. The highest OLP
yield is obtained by the cracking process using the RFCC-S
catalyst while the gas yield is the lowest. The highest gas yield
is obtained by the cracking process using the HY catalyst. The
conversion of triglyceride from palm oil over different catalysts
is clearly different for each catalyst used, where the commercial
HY catalyst shows the highest conversion. The triglyceride
conversion is close to 100% over the HY catalyst. However, the
conversion of triglyceride from palm oil over the acid-treated
RFCC catalyst is still lower than conversion over the HY
catalyst. The closest conversion of palm oil over the acid-
treated RFCC catalyst is obtained by the RFCC-M catalyst.
As presented in Figure 6, the highest palm oil conversion
showed on the RFCC-M catalyst may be because of the role of
catalyst acid site concentration (quantity and type). The
catalyst acidity is the most important factor that affects the
conversion of palm oil through catalytic cracking, as reported
by Jiao et al.39 As reported in the pyridine-FTIR analysis
section (Table 4 and Figure 4), the RFCC-M catalyst shows
the highest palm oil conversion because of high acid (Brønsted
and Lewis) site amount/concentration as the active site for the
catalytic cracking reaction. The acid sites lead to the
carbocation formation that is the initiation process of cracking
reaction, as suggested by Corma and Orchillés.17 The more the
acid sites present on the catalyst, the higher possibility of
carbocation formation occurred. Therefore, the higher palm oil
conversion can be easily achieved by using the enhanced
Brønsted and Lewis acid sites. However, the conversion of
palm oil over the RFCC-C catalyst is slightly higher than the
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conversion over the other spent RFCC catalysts, although the
acid amount of the RFCC-C catalyst is lower than that of other
spent RFCC catalysts. By the fact that the RFCC-C catalyst
has higher both surface area and pore volume, it can be
suggested that the higher palm oil conversion when using the
RFCC-C catalyst is because of its higher surface area and pore
volume. The same phenomenon is shown by the commercial
HY-zeolite catalyst. As shown in Figure 6, interestingly, the
conversion of triglyceride from palm oil over the HY catalyst is
the highest, even though it has the lowest total acid site
amounts. The high conversion value over the HY catalyst is
caused by its higher surface area (Table 3). It is true that the
higher surface area of the catalyst can assist the reactant
molecules to be easily adsorbed on the active sites because of
the reduction of mass transfer limitation over the catalysts
having higher surface area.14 The highest the surface area of
catalysts, the highest the possibility of the adsorption process
of reactants on the active sites.
The lowest yield of carbon−coke is shown by the RFCC-C
catalyst while the highest carbon−coke yield is demonstrated
by the commercial HY-zeolite catalyst. Based on the pyridine-
probed FTIR analysis (Table 4 and Figure 4), each catalyst has
different Brønsted to Lewis acid site ratios. The highest
carbon−coke yield on the HY catalyst is because of its lowest
Brønsted to Lewis acid site ratio and highest surface area. It
seems that the carbon−coke yield is directly proportional to
the Lewis acid site amount. Therefore, it is suggested that the
Lewis acid site on the catalyst leads to the coke formation, as
reported previously through excessive hydrogen transfer
reactions.40,41 The carbon−coke formation during catalytic
cracking reaction affects the catalyst surface area, as provided
in Table 5 with respect to the used catalyst. The used catalysts
Table 5. Surface Area of the Used Acid-Treated RFCC
Catalysts
used catalysts surface area (m2/g) surface area reduction (%)
RFCC 19.78 81.63
RFCC-C 19.25 86.71
RFCC-S 11.56 84.67
RFCC-M 5.75 95.56
were washed using n-hexane through the Soxhlet method and
dried at 110 °C for 6 h before analysis. Compared to Table 3,
the surface area of the used catalysts (Table 5) decreases
significantly after cracking reaction process because of carbon−
coke formation. Therefore, it is suggested that decrease in the
used acid-treated RFCC catalyst surface area is because of the
pore blocking by carbon−coke.
Liquid fuels produced from the palm oil catalytic cracking
over the HY and the acid-treated spent RFCC catalysts mainly
contains of gasoline, kerosene, and diesel fraction. These
fractions were classified by the carbon contents. All of the C5−
C12 components, including oxygenated components, were
grouped into the gasoline fraction, the C13−C14 components
were classified as the kerosene fraction, and the C15−C18
components were classified as the diesel fraction.14,42 Based
on Figure 7, the distribution of these fuel fractions is different
in accordance with the different catalysts used. It is strongly
confirmed that the RFCC-S catalyst shows the highest diesel
yield but the lowest gasoline yield. This fact leads to the
formation of long-chain hydrocarbon fraction rather than the
short-chain hydrocarbon fraction. The formation of long-chain
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

deactivation through carbon−coke formation on the surface

of catalysts.44 The formation of hydrocarbon, alcohol, and
ketone compounds indicates that some of the oxygen atoms in
triglyceride from palm oil had been removed through a series
of reactions, such as deoxygenation.8
As shown in Table 6, the highest hydrocarbon fraction is
showed by the RFCC-M catalyst while the lowest hydrocarbon
fraction is obtained by the RFCC-S catalyst. The hydrocarbon
fraction is in line with the acid amount of catalysts, including
acidity and acid types. The highest hydrocarbon fraction in the
liquid product is obtained by RFCC-M, showing the highest
total acid amount. However, the total acid amount is not only
the main factor affecting the formation of hydrocarbon
fraction. The lowest hydrocarbon fraction is showed by the
RFCC-S catalyst, suggesting high total acid amount. Moreover,
the HY catalyst that has the lowest total acid amount can
Figure 7. Distribution of product selectivity of gasoline, kerosene, and
produce the high hydrocarbon fraction. Therefore, it is
diesel ranges. suggested that the type of acid sites on the catalyst also
affected the hydrocarbon fraction formation in the liquid
hydrocarbon fraction over the RFCC-S catalyst is because of its product.
high Brønsted to Lewis acid ratio. With respect to other As shown in Tables 4 and 6, the hydrocarbon fraction in the
catalysts used, it is shown that the OLP product selectivity liquid fuel product is inversely proportional to the Brønsted to
distribution mainly depends on the Brønsted and Lewis acid Lewis acid site ratio or directly proportional to the Lewis acid
site amount present on the catalysts. Increasing the Brønsted site amount. The RFCC-S catalyst contains the highest
acid site amount on the catalyst pronounces to the selectivity Brønsted to Lewis acid ratio, meaning that the Brønsted acid
of long-chain hydrocarbons increases and the selectivity of site is dominant on the catalyst, presenting the lowest
short-chain hydrocarbon decreases. On the other hand, hydrocarbon fraction in the liquid fuel product. On the other
increasing the Lewis acid site amount leads to higher selectivity hand, the commercial HY zeolite catalyst having the lowest
of short-chain hydrocarbons and lower selectivity of long-chain Brønsted to Lewis acid site ratio results in the high
hydrocarbons, as suggested by Fan et al.28,43 hydrocarbon fraction. Furthermore, the oxygen removed in
3.3. Effect of Catalyst Type on the Component the biofuels (Table 6) seems proportional to the Lewis acid
Composition of the Liquid Product. Based on GC−MS site amounts. Therefore, it suggested that the Lewis acid site
analysis, the main components of liquid product of palm oil can promote the deoxygenation reaction on the catalytic
cracking are classified into seven groups including, hydro- cracking process of palm oil into biofuels. As reported by
carbons, acids, alcohols, aldehyde, esters, ketones, and glycerol, Rogers and Zheng,45 the Lewis acid site can promote indirect
as listed in Table 6. As expected, the hydrocarbon fraction is decarbonylation reaction. Hewer et al.46 also reported that the
proportion of Lewis to Brønsted acid sites has strong influence
Table 6. Distributions of Components in the Biofuels on the selectivity of the hydrodeoxygenation reaction. Li et al.6
reported that the hydrocarbon production could be improved
composition (%) significantly by increasing the acidic sites of ZSM-5 through
components HY RFCC-N RFCC-C RFCC-S RFCC-M decarbonylation, cracking, and aromatization reactions. How-
hydrocarbons 77.72 66.31 65.24 56.99 91.39 ever, the high catalyst acidity also leads to high affinity for
acids 4.86 19.54 17.48 15.69 4.42 carbon−coke formation.40,41 Therefore, it is suggested that the
alcohols 2.40 10.35 7.41 7.55 2.65 synergistic roles of both sulfuric acid and citric acid increase
aldehydes 0 0 0 2.18 1.57 the acid site amounts of the spent RFCC catalyst through the
esters 2.33 1.57 3.84 17.6 0 generation of both Brønsted and Lewis acid sites, which can
ketones 12.69 0 3.31 0 0 positively promote the formation of hydrocarbon fraction in
glycerol 0 2.24 2.74 0 0 the liquid fuel product on the palm oil catalytic cracking.
oxygen contenta (%) 1.83 4.04 4.37 4.41 0.99 Concerning the deoxygenation reaction occurred, the
oxygen removeda 78.93 53.63 49.86 49.34 88.64 compound composition of biofuel products using GC−MS
(%) (Table S1 Supporting Information) was used to study this
a
Calculated from GC−MS analysis. matter. The deoxygenation process of vegetable oils (fatty
acids) can take place through decarboxylation/decarbonylation
the most dominant components in the liquid product. Similar reaction.47,48 In the main reaction pathway in deoxygenation of
finding was obtained by Zhao et al.44 that the liquid product fatty acids, the obtained products are hydrocarbons that have
from catalytic cracking of carinata oil using the Zn/Na-ZSM-5 one carbon shorter compared to the fatty acid in the liquid
catalyst contained hydrocarbon and oxygenated compounds, in product and carbon monoxide (CO) and carbon dioxide
which hydrocarbons were the dominant compounds found. (CO2) in the gas phase.49 Because the main fatty acid
The other fractions found in the liquid products obtained by components of palm oil (Table 1) are palmitic acid, the
all catalysts used in this study are acid and alcohol fractions. products of deoxygenation process through decarboxylation/
The presence of acids and esters in the liquid product suggests decarbonylation reaction should be pentadecane and/or
that some portions of triglyceride molecules from palm oil are pentadecene, as displayed in Figure 8. According to the result
not completely catalytically cracked because of catalyst of GC−MS analysis (Table S1 and Figure S2a−e of
9465 https://dx.doi.org/10.1021/acs.iecr.0c01061
Ind. Eng. Chem. Res. 2020, 59, 9459−9468
Industrial & Engineering Chemistry Research
Figure 8. Reaction scheme for deoxygenation of palmitic acid to
pentadecane and pentadecene.
Supporting Information), these components appear in the
biofuel product from cracking process by all catalysts except
the RFCC-S catalyst. As can be seen, the RFCC-S catalyst has
low activity to convert palmitic acid (hexadecenoic acid)
because the palmitic acid still detected in the liquid products.
Even though, these facts confirm that acid-treated spent RFCC
catalysts are potential for deoxygenation reaction. Further-
more, the acid-treated spent RFCC catalysts are effective in
decarboxylation reaction of palmitic acid (Table S1 Supporting
Information). Interestingly, n-pentadecane is not formed by
the HY catalyst; however, 1-pentadecene appears instead. It
confirms that the HY catalyst leads to decarbonylation
reaction. Moreover, according to the result of GC−MS
analysis (Table S1 Supporting Information), the HY catalyst
produces more n-heptadecane and isomerized heptadecene (1-
heptadecene and 8-heptadecene). This fact agrees that the HY
zeolite prefers to decarbonylation reaction because of the
presence of Lewis acid site on the HY catalyst.45 With respect
to the longer hydrocarbon compounds being formed, it
suggested that these compounds are formed through cracking
reaction of higher/longer carbon compounds in the palm oil
(Table 1).
3.4. Catalyst Stability Test. The long-term catalyst
stability is an important parameter in catalytic cracking process
of palm oil, especially for industrial practice. In this study, the
stability test was conducted in order to investigate the acid-
treated spent RFCC catalyst stability in palm oil catalytic
cracking reaction. The RFCC-S catalyst was chosen for
stability test because of its high resistance of coke formation
(Figure 6) indicated by the lowest surface area reduction
(Table 5). The RFCC-S catalyst was performed in palm oil
catalytic reaction at 450 °C with a WHSV of 0.365 min−1 for
20.75 h (1245 min). The yield of OLP and selectivity of
gasoline were monitored every 2 h in order to investigate the
RFCC-S catalyst stability. Figure 9 shows the stability test
result of RFCC-S catalyst in palm oil catalytic cracking reaction
Figure 9. Stability test of the RFCC-S catalyst in palm oil catalytic
cracking reaction.
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into biofuels. Generally, as can be seen in Figure 9, the yield of
OLP decreases slightly and remains constant after 8.5 h.
Furthermore, the selectivity of gasoline remains constant as
well. These facts confirm that the RFCC-S catalyst has high
stability because of its high resistance of coke formation.
4. CONCLUSIONS
The waste of spent RFCC catalyst can still be reutilized as a
catalyst for cracking palm oil to liquid fuels by regenerating and
enhancing the catalyst acid (Brønsted and/or Lewis) sites, as
both acid sites contributed significantly as active sites on the
catalytic cracking reaction. The acidity enhancement of the
spent RFCC catalyst could be performed through the catalyst
modification by using acid (citric acid and/or sulfuric acid)
treatment. The Brønsted acid site increased during sulfuric acid
treatment or mixed citric−sulfuric acid treatment because of
the proton transfer from the acid and/or because of the
formation of sulfate groups (HOSO3−) on the catalyst. The
synergistic effect of both sulfuric and citric acid caused the
regeneration of both Brønsted and Lewis acid sites, which
affects the catalyst performance, on the catalytic cracking
reaction of palm oil into the liquid fuel product. The
conversion of palm oil or triglyceride increased with acidity
of catalysts. The spent RFCC catalyst treated by sulfuric acid
(RFCC-S) showed the highest Brønsted to Lewis acid ratio
while the spent RFCC catalyst treated by mixed sulfuric−citric
acids led to the highest total acidity. The product component
distribution depended mainly on the Brønsted to Lewis acid
ratio of the spent RFCC catalyst. With respect to the palm oil
cracking to produce hydrocarbon fuels, the Brønsted acid site
on the catalyst led to the long-chain hydrocarbons while the
Lewis acid site on the catalyst convinced the formation of coke
and short-chain hydrocarbons. Moreover, the formation of
hydrocarbon fraction in the liquid product depended on the
total acid site/acidity and the amount of Lewis acid site
(Brønsted to Lewis acid ratio) on the catalysts.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.0c01061.
Identification of compounds’ composition of the liquid
fuel product using GC−MS and GC−MS analysis of
biofuels or liquid products and palm oil (PDF)
■ AUTHOR INFORMATION
Corresponding Author
I. Istadi − Department of Chemical Engineering, Faculty of
Engineering, Diponegoro University, Semarang, Central Java
50275, Indonesia; orcid.org/0000-0002-2914-3545;
Email: istadi@che.undip.ac.id
Authors
Teguh Riyanto − Department of Chemical Engineering, Faculty
of Engineering, Diponegoro University, Semarang, Central Java
50275, Indonesia
Luqman Buchori − Department of Chemical Engineering,
Faculty of Engineering, Diponegoro University, Semarang,
Central Java 50275, Indonesia
Didi Dwi Anggoro − Department of Chemical Engineering,
Faculty of Engineering, Diponegoro University, Semarang,
Central Java 50275, Indonesia
https://dx.doi.org/10.1021/acs.iecr.0c01061
Ind. Eng. Chem. Res. 2020, 59, 9459−9468
Industrial & Engineering Chemistry Research
G. Gilbert − Department of Chemical Engineering, Faculty of
Engineering, Diponegoro University, Semarang, Central Java
50275, Indonesia
Kania Adelia Meiranti − Department of Chemical Engineering,
Faculty of Engineering, Diponegoro University, Semarang,
Central Java 50275, Indonesia
Elok Khofiyanida − Department of Chemical Engineering,
Faculty of Engineering, Diponegoro University, Semarang,
Central Java 50275, Indonesia
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c01061
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to express their sincere gratitude to the
Research Institution and Community Service, Diponegoro
University, Semarang, Indonesia for financial support received
under the research project of Riset Publikasi Internasional
Bereputasi Tinggi (RPIBT) with contract number: 387-07/
UN7.P4.3/PP/2018.
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