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Catalytic conversion of palm oil over mesoporous

aluminosilicate MCM-41 for the production


of liquid hydrocarbon fuels
Farouq A. Twaiq
a
, Noor Asmawati M. Zabidi
b
,
Abdul Rahman Mohamed
a
, Subhash Bhatia
a,
*
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal,
SPS, Pinang, Malaysia
b
Universiti Teknologi Petronas, Sri Iskandar, 31750 Tronoh, Perak, Malaysia
Accepted 31 January 2003
Abstract
The catalytic cracking of palm oil to liquid hydrocarbon fuels was studied in a fixed bed micro-
reactor operated at atmospheric pressure, reaction temperature of 723 K and weight hourly space
velocity (WHSV) of 2.5 h
1
over the synthesized mesoporous molecular sieve MCM-41 materials.
Mesoporous aluminosilicate with Si/Al ratio of 50 was synthesized using the hydrothermal method.
Different pore sizes were obtained by changing the type of template and organic directing agent
(ODA) used. The synthesized materials were characterized using various analytical methods such as
X-ray powder diffraction (XRD), BET surface area, inductive coupled plasma (ICP), MAS NMR,
FTIR and temperature-programmed desorption (TPD). The materials exhibit a crystalline structure of
MCM-41 mesoporous molecular sieves with surface area varyng from 550 to 1200 m
2
/g and an
average pore size (APS) ranging from 1.8 to 2.8 nm. The synthesized MCM-41 catalysts show high
activity for palm oil cracking. The conversion of palm kernel oil, lower-molecular-weight oil, was
higher as compared to higher-molecular-weight, palm olein oil. MCM-41 materials were selective
for the formation of linear hydrocarbons, particularly, C
13
when palm kernel oil was used and C
17
when palm olein oil was fed. The yield of liquid product decreased with the increase of surface area
of the catalyst. The gasoline selectivity increased whereas diesel selectivity decreased with the
conversion of palm oil.
D 2003 Elsevier Science B.V. All rights reserved.
Keywords: Catalytic cracking; Hydrothermal synthesis; Palm oil; Mesoporous molecular sieve catalyst
0378-3820/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0378-3820(03)00048-1
* Corresponding author. Tel.: +60-4-593-7788; fax: +60-4-594-1013.
E-mail address: chbhatia@eng.usm.my (S. Bhatia).
www.elsevier.com/locate/fuproc
Fuel Processing Technology 84 (2003) 105120
1. Introduction
Conversion of plant oil to fuels has been investigated for the last 10 years [1]. Processes
utilizing zeolites have been found effective for the production of a variety of liquid
hydrocarbon fuels from plant oils [2]. Improved results were obtained with catalytic
cracking of plant oils if the crystalline shape-selective medium-pore-size microporous
zeolite (e.g. HZSM-5) is used.
Malaysia is one of the large producers of palm oil. In 2001, the crude palm oil
production was about 13 million tons. Palm oil can be converted to clean premium
transportation fuels and chemicals. Catalytic cracking of palm oil over HZSM-5 gave high
yield of gasoline with high aromatics content [3]. However, the selectivity for gaseous
products was high and more liquid products desired. The need for solid acid catalysts with
large pores has initiated research in this direction and resulted in the discovery of the
M41S mesoporous family [4,5]. To improve the production of gasoline and total yield of
organic liquid product (OLP) in the catalytic cracking of palm oil, the mesoporous catalyst
MCM-41 is chosen in this research work. MCM-41 has been reported as a selective
catalyst for the cracking of naphtha [6]. Comparing the performance of MCM-41 to
medium-pore zeolites, such as ZSM-5, it was found that the MCM-41 is more selective for
C
5
+
olefinic products. These olefinic products are used in alkylation and etherification
processes to produce high-octane fuels [7]. Al-MCM-41 has been reported as an acid-
cracking catalyst for many reactions such as the cracking of recycled plastic wastes [8],
catalytic cracking of n-hexadecane and isomerization of n-hexane [9,10].
The objective of the present study is to investigate the effect of surface area and average
pore size of MCM-41 on the conversion of palm oil and distribution of liquid hydro-
carbons products. In order to produce MCM-41 materials with different pore sizes, three
techniques are used: (1) by altering the chain length of the surfactant; (2) addition of an
auxiliary organic and (3) by post-synthesis treatment to reduce the pore size [5,11]. It is
possible to select and prepare a particular pore size by judicious choice of surfactant [12].
The properties of MCM-41 materials depend on the source of silica (fumed or fused) and
the synthesis process parameters, such as the gel ageing time, temperature, duration of
synthesis and pH of the gel [13].
2. Experimental
2.1. Catalyst preparation
Aluminum-containing (Si/Al = 50) mesoporous material was synthesized by hydro-
thermal treatment of reaction gel mixture. Twelve samples of Al-containing mesoporous
material were prepared using different surfactant template (T) and organic directing agent
(ODA) at different T/Si ratios as shown in Table 1. A solution of the surfactant template
and the ODAwas prepared in a desired ratio in a Pyrex vessel at room temperature. NaOH
(0.2 g) and 0.186 g of sodium aluminate (Al
2
O
3
Na
2
O) were added to the solution
containing the template and ODA. Cab-osil M5 (5.0 g; Fluka) was added to the solution.
The mixture was vigorously stirred for 1 h using a magnetic stirrer. The pH of the solution
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 106
was maintained around 13.8. The gel formed was transferred to a 400-ml Teflon-lined
stainless steel Parr-reactor (Model No. 4842) and stirred continuously at 50 rpm for 24 h at
423 K for crystallization to take place. The precipitate was filtered, washed with deionized
water and kept overnight at room temperature, then calcined at 813 K for 6 h in a muffle
furnace. The resultant material (Na-form) was converted to H-form by refluxing the
sample at 353 K in the presence of 0.1 N aqueous NH
4
Cl solutions with liquid/solid ratio
of 20 and continuous stirring for 24 h. The resultant solid was filtered and washed with
deionized water until chloride ions were not detected in the filtrate. The sample was kept at
room temperature and then calcined at 813 K for 4 h.
2.2. Characterization
X-ray powder diffraction (XRD) analysis of the calcined samples was performed on a
Philips powder diffractometer (Model PW 1820) using Cu-Ka radiation (40 kV, 40 mA).
The XRD spectra in the range of 1.5j10j were obtained at a step size of 0.04 for 10 s.
The BET surface area and average pore size (APS) of the samples were determined by
nitrogen adsorption at 77 K using Quanta chrome Autosorb-1 equipment. The Si/Al
ratios of the synthesized materials were analyzed using an inductive coupled plasma
(ICP) spectrometer (PE, Optima 3000).
27
Al NMR spectra were obtained using a Varian
Jakobsen-style MAS probe (5 mm) operated at 8 kHz. FT-IR technique was employed to
determine the nature of acid sites (Lewis and Bronsted types) present on the pyridine-
adsorbed samples using a Perkin-Elmer FTIR (Model 2000). The IR spectra of the
catalysts were scanned for recording bands in the region of 14001650 cm
1
. The
temperature-programmed desorption of ammonia was performed using a Chembet 3000
instrument (Quanta chrome). A 0.05-g sample was activated at 773 K for 1 h with
helium (99.9% purity, MOX) flowing at 60 ml/min followed by adsorption of 1%
ammonia in helium for 1 h at room temperature. The ammonia was desorbed by heating
the sample in flowing helium from ambient to 973 K at 10 K/min. The desorption peak
Table 1
Compositions of the synthesis gel for aluminosilicate (Si/Al = 50) mesoporous materials prepared by
hydrothermal treatment
Catalyst ID Template (T) Organic directing agent
(ODA)
T/Si ODA/T
MM-1 C
12
TMA-OH 0.25 0.0
MM-2 C
12
TMA-OH TMA-OH 0.25 1.0
MM-3 C
12
TMA-OH TEA-OH 0.25 1.0
MM-4 C
12
TMA-OH 0.125 0.0
MM-5 C
12
TMA-OH TMA-OH 0.125 1.0
MM-6 C
12
TMA-OH TEA-OH 0.125 1.0
MM-7 C
16
TMA-OH 0.5 0.0
MM-8 C
16
TMA-OH TMA-OH 0.5 0.5
MM-9 C
16
TMA-OH TEA-OH 0.5 0.5
MM-10 C
16
TMA-OH 0.25 0.0
MM-11 C
16
TMA-OH TMA-OH 0.25 0.5
MM-12 C
16
TMA-OH TEA-OH 0.25 0.5
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 107
areas were normalized using the TPRWin, version 1 software and used to calculate the
acidity.
2.3. Catalytic cracking of palm oil
In the present study, the palm oil used was refined, bleached and deodorized oil. The
palm olein was obtained from Agriculture Oils Sdn. Bhd. (Penang, Malaysia) and palm







Fig. 1. Micro-reactor rig used in the catalytic conversion of palm oil.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 108
kernel oil was obtained from Acid Chem International Sdn. Bhd. (Penang, Malaysia). Palm
olein oil consisted mainly of 42% C16 and 54% C18 fatty glycerides. The palm kernel oil
contained 50% C12, 16% C14, 8% C16 and 20% C18 fatty glycerides. The palm oil
cracking was performed at atmospheric pressure, reaction temperature of 723 K with palm
oil feed rate (WHSV) of 2.5 h
1
and oil/catalyst ratio of 7.2. Calcined powder (1.0 g),
MCM-41 catalyst of particle size <32 Am was loaded over 0.2 g quartz wool supported
over stainless steel mesh surface in a stainless steel reactor (150 mm long and 10 mm ID).
Fig. 1 shows the experimental setup used in the cracking process. The reactor was heated to
the desired reaction temperature using a vertical tube furnace under nitrogen gas flowing at
a rate of 100 ml/min. Once the temperature was stabilized, palm oil was fed using a syringe
pump (Model No. E-74900-05, Cole-Parmer). The products leaving the reactor were cooled
to 313 K in the condenser system in order to prevent solidification of the residual oil. A
schematic diagram of the process is shown in Fig. 2. The gaseous products were collected in
a gas sampler and the total gas evolved during the experiment was monitored using water
displacement. The condensed liquid products were collected in a liquid sampler at room
temperature. The samples were collected once steady state was reached. The reactor was
flushed by 30 ml/min nitrogen gas for 30 min to remove the remainder products from the
reactor. The aqueous phase was separated from the condensed liquid products using a
syringe. The liquid product was distilled in a vacuum microdistillation unit at 100 Pa and
473 K for 30 min. The distillate fraction was the organic liquid product (OLP) and the pitch
was assumed to be the residual oil. In order to determine the products that remained in the
system, the catalyst was washed with acetone and then dried in an oven at 373 K for 1 h
prior to coke analysis.
Fig. 2. Schematic diagram for the collection and analysis of various products from palm oil over zeolite catalyst.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 109
2.4. Products analysis
The gaseous products (C
1
C
5
, H
2
, CO and CO
2
) were analyzed with a gas chromato-
graph (Hewlett Packard, Model No. 5890 series II) using an HP Plot Q capillary glass
column (Divinyl benzene/styrene porous polymer, 30 m long 0.53 mm ID40 Am film
thickness). The gas chromatograph was equipped with a thermal conductivity detector
(TCD) and nitrogen was used as a carrier gas. The organic liquid product (OLP) was
analyzed on a capillary glass column (Petrocol DH 50.2, film thickness 0.5 Am, 50 m
long 0.2 mm ID) at a split ratio of 1:100, using the FID detector. The oven temperature
was programmed at a heating rate of 4 K/min in the range of 333523 K. The
compositions of OLP were defined according to the boiling point range of petroleum
products such as gasoline (333408 K), kerosene (408443 K) and diesel (443473 K).
The coke formed over the catalyst during the cracking reaction was determined by
thermal gravimetric analyzer (Perkin-Elmer TGA 7). About 5 mg of acetone-washed spent
catalyst sample was subjected to TG analysis at temperature program of 20 K/min. The
sample was heated from ambient to 373 K under nitrogen gas flowing at 30 ml/min. It was
kept at 373 K for 10 min in order to remove the volatile materials. The sample was then
heated to 973 K with oxygen gas flowing at 30 ml/min.
3. Results and discussion
3.1. Characterization
Samples coded as MM-1 to MM-6 were synthesized using C
12
TMA as template. The
C
16
TMA was used as a template for samples coded MM-7 to MM-12. Table 2 shows the
lattice parameter a
o
(a
o
= 2d
100
/M3) obtained from the powder XRD patterns of meso-
porous MCM-41 material samples. When the template chain length was changed from C
12
Table 2
Textural properties of MCM-41 mesoporous materials
Catalyst ID Si/Al a
o
(nm) APS BJH
method
(nm)
Pore volume
(cm
3
/g)
p/p
o
=0.5
Surface area
(calcined)
(m
2
/g)
MM-1 67 4.28 2.07 0.220 1080
MM-2 53 4.13 1.93 0.308 930
MM-3 55 3.78 1.92 0.641 1240
MM-4 77 4.37 2.19 0.600 990
MM-5 64 3.97 1.93 0.501 990
MM-6 63 3.72 1.85 0.508 1085
MM-7 50 5.39 2.74 0.524 580
MM-8 51 4.56 2.32 0.639 1025
MM-9 85 4.55 2.30 0.433 880
MM-10 61 4.65 2.73 0.835 1160
MM-11 66 4.67 2.73 0.703 1250
MM-12 67 4.62 2.60 0.680 1150
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 110
to C
16
, a
o
increased from 3.72 to 4.62 nm. When C
12
TMA template was used, the addition
of organic directing agent (ODA) decreased the value of a
o
, however, such effects were
not observed for C
16
TMA. The BET surface area, pore volume and average pore size data
are presented in Table 2. The average pore size was calculated from adsorption data using
the Barrett, Joyner and Halenda (BJH) method. The lower T/Si ratio gave higher pore
volume and surface area. The pore size decreased from 2.8 to 2.5 nm with the addition of
0.5 mol of TMA. With the use of lower molar ratio of T/Si (with C
16
TMA), the pore size
did not change with the addition of ODA, but the pore volume decreased and the pore
distribution became wider. The addition of ODA to C
12
TMA decreased the pore size from
2.2 to about 1.9 nm. When C
16
TMAwas used as template, it was observed that decreasing
the T/Si ratio resulted in a narrower pore distribution and a higher pore volume.
The elemental compositions and textural properties of the synthesized materials are
presented in Table 2. NMR study was performed to determine the status of the Al
incorporated in the MCM-41 material. Fig. 3 shows the
27
Al MAS NMR spectra of MCM-
41 sample. The sharp peak at around 50 ppm was due to the presence of tetrahedral Al in
the framework. The peak at 0 ppm was ascribed to octahedral coordinated nonframework
aluminum. Acidity of the hydrogen form MCM-41 was determined by temperature-
programmed desorption (TPD) of ammonia, and the results are shown in Fig. 4. For
comparison purposes, the desorption curve of NH
3
from HZSM-5 is also shown in Fig. 4.
Zeolite HZSM-5 (Si/Al = 50) shows a weak acidity peak at temperature of 433 K and a
strong acidity peak at 673 K. The desorption peak at 443 K was referred as the weak acid
site of H-MCM-41. The type of acid sites (Lewis and Bronsted) was evaluated by
adsorption of pyridine at 423 K followed by FTIR analysis of the MCM-41 samples. Fig. 5
shows the FTIR spectrum of the pyridine-adsorbed H-MCM-41 sample (MM-12). The
peak at 1600 cm
1
was due to the hydrogen-bonded pyridine. Pyridine bound to Bronsted
acid sites gave peaks at 1546 and 1640 cm
1
, respectively, whereas those bound to Lewis
sites are detected at 1450 cm
1
. The peak at 1490 cm
1
was attributed to pyridine
associated with both Lewis and Bronsted acid sites.
Fig. 3.
27
Al MAS NMR spectrum of MM-12.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 111
Fig. 5. FTIR spectrum of MM-12.
Fig. 4. Temperature-programmed desorption (TPD) of NH
3
from MM-12 and HZSM-5 (Si/Al = 50).
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 112
3.2. Catalytic activity
Palm kernel oil and palm olein oil having different molecular weight in their
triglyceride structure were used to study the activity and selectivity of H-MCM-41 having
different pore sizes. The synthesized MCM-41 catalyst samples were converted into H-
form in order to increase the acidity of the catalyst. The catalytic cracking of palm oil over
H-MCM-41 sample was performed at 723 K and weight hourly space velocity (WHSV) of
2.5 h
1
in a micro-reactor at Oil/Cat ratio of 7.2. The performance of H-MCM-41
catalysts having different pore sizes was studied in terms of conversion and yield of liquid
hydrocarbon products. Tables 3 and 4 show the conversion and yield of products for palm
Table 3
Catalytic cracking of palm kernel oil over mesoporous aluminosilicate materials having different pore size
distribution
Catalyst Conversion Yield
of gas
Yield of
gasoline
Yield of
kerosene
Yield of
diesel
Yield of
water
Yield of
coke
Empty reactor 42.00 4.90 14.80 7.20 15.10 0.00 0.00
MM-1 86.49 2.97 19.52 17.81 44.50 1.70 6.67
MM-2 97.72 11.13 42.54 29.90 14.16 0.00 8.33
MM-3 92.14 12.83 21.40 23.88 25.68 8.33 11.94
MM-4 88.13 9.18 29.02 31.28 10.31 8.33 5.83
MM-5 91.18 8.94 27.55 28.57 20.05 6.09 7.78
MM-6 94.15 8.62 36.02 25.67 14.94 8.89 11.39
MM-7 84.95 7.02 17.17 13.17 39.73 7.86 7.64
MM-8 95.49 9.96 50.85 22.15 9.75 2.78 12.08
MM-9 96.44 9.30 30.19 30.43 20.97 5.56 12.08
MM-10 95.99 12.54 36.45 23.87 17.06 6.07 14.44
MM-11 94.04 11.33 43.42 22.73 12.23 4.33 17.50
MM-12 92.13 9.65 36.79 24.32 14.90 6.47 11.81
Table 4
Catalytic cracking of palm olein oil over mesoporous aluminosilicate materials having different pore size
distribution
Catalyst Conversion Yield
of gas
Yield of
gasoline
Yield of
kerosene
Yield of
diesel
Yield of
water
Yield of
coke
Empty reactor 38.50 4.70 12.10 6.50 15.20 0.00 0.00
MM-1 75.59 9.99 25.19 10.54 22.85 7.02 12.08
MM-2 63.34 8.61 16.16 9.03 22.33 7.21 12.64
MM-3 72.93 8.06 23.23 12.11 22.31 7.21 11.53
MM-4 81.80 7.48 31.43 12.64 24.26 5.99 7.78
MM-5 82.67 8.21 25.06 13.28 30.13 5.99 11.11
MM-6 80.91 0.00 28.17 14.76 31.99 5.99 11.11
MM-7 83.71 8.45 36.73 12.70 19.23 6.60 8.75
MM-8 92.40 6.86 42.58 20.12 10.57 2.78 9.49
MM-9 73.80 8.64 24.61 11.51 22.61 6.43 9.17
MM-10 88.05 10.78 36.91 12.30 22.32 5.74 11.67
MM-11 82.85 8.72 32.66 11.03 25.66 4.78 8.19
MM-12 90.12 21.83 43.30 10.98 9.58 4.43 12.22
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 113
kernel oil and palm olein oil, respectively, over different H-MCM-41 catalysts. Tables 3
and 4 present the conversion and yield of products for palm kernel oil and palm olein oil
over aluminosilicate MCM-41 catalysts, respectively. Selectivity to linear C
17
, C
15
and C
13
hydrocarbon with 1020 wt.% of the OLP was observed. The presence of linear
hydrocarbons in the products related to the low shape selectivity of the catalyst due to
the large size of the pores compared to the size of the products. The C
17
hydrocarbons are
close to the size of the fatty acid molecules from palm oil. The weak acidity of the
mesoporous material probably affected the ester group faster than the cracking reaction at
high temperature by extracting CO
2
from the ester. The cracking reaction occurred as
secondary cracking reaction of the linear chain, which has the length of C
13
C
17
depending on the type of the oil.
In order to determine the extent of thermal cracking of palm oil, a blank run was
performed in an empty reactor containing quartz wool. Low conversion of palm oil was
observed at 623 K (5 wt.%). The conversion of palm oil in an empty reactor at 723 K and
WHSV of 2.5 h
1
was about 40 wt.%. The yield of gaseous product was about 5 wt.%
which contains 10% CO
2
, 20% ethane and ethylene, 40% propylene and 25% C
4
+
. The
liquid product contains about 40% hydrocarbons in the gasoline boiling range, 20%
kerosene, 40% diesel and no aromatics were detected.
Fig. 6. The effect of palm oil feed type of the conversion and liquid products distribution.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 114
The conversion of palm oil was increased with the increase in surface area of the
catalysts. The conversion of palm olein was found lower as compared to palm kernel oil.
The palm olein oil has larger molecule size and thereby gave lower conversion probably
due to diffusion resistance. When the palm oil was cracked over catalysts prepared using
C
12
TMA, the gaseous products were almost constant (812 wt.%) but the OLP yield
was decreased with increase in surface area. The gaseous product and OLP yield
increased with surface area over the catalysts prepared using C
16
TMA. The liquid
products obtained from palm oil cracking were compared to the product analysis
obtained from petroleum cracking and found to contain high amount of linear hydro-
carbons. The coke formation from palm kernel oil cracking was increased with increase
of surface area of the catalyst. The coke formation was lower from palm olein oil
compared to that of palm kernel oil and was about 1012 wt.%. The coke formation
obtained from the cracking of palm oils over mesoporous materials were much higher
compare to the zeolites.
Fig. 7. Effect of the surface area of mesoporous aluminosilicate catalyst on the selectivity of total products from
cracking of palm oil kernel (a) prepared using C
12
TMA (b) prepared using C
16
TMA.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 115
It has been reported in the literature [10] that MCM-41 has lower activity when small-
size molecule such as n-heptane was cracked. When large molecule such as gas oil was
cracked, MCM-41 activity was found to be the same as the activity of zeolite USY [11]. The
cracking of palm oil over MCM-41 was found much similar to those reported with USY
zeolite [1]. The cracking of palm kernel oil was found different compared to palm olein oil
over MCM-41 catalyst. However, over other zeolite catalysts, the cracking pattern of palm
olein was found same as palm kernel oil.
Fig. 6a and b shows the relation between the yields of liquid products against the
conversion obtained over different MCM-41 catalysts for both palm kernel and palm olein
oils, respectively. The conversion of palm kernel oil (average carbon number of 38) was
8598 wt.%, whereas the palm olein (average carbon number of 54) gave 6292 wt.%
conversion over the same catalysts. The cracking of palm kernel oil was easier because of
easy accessibility of oil into the pores of the catalysts. The yield of gasoline and kerosene
were observed to increase with increase of conversion. The increase in gasoline yield was
much higher compared to the kerosene. The yield of diesel was observed to increase when
the conversion was lower than 80 wt.% when palm olein was cracked. The yield of diesel
Fig. 8. Effect of the surface area of mesoporous aluminosilicate catalyst on the selectivity of liquid products from
cracking of palm oil kernel (a) prepared using C
12
TMA (b) prepared using C
16
TMA.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 116
decreased with conversion when the conversion was higher than 80 wt.% showing the
effect of secondary cracking reactions which led to cracking of diesel into smaller
components in gasoline boiling range.
The catalysts coded MM-1 to MM-6 have pore sizes in the range of 1.82.2 nm with
different surface areas and pore volumes. Conversion (94 wt.%) was obtained over catalyst
with average pore size (APS) of 1.85 nm, and dropped to 80 wt.% for catalyst having APS
of 2.2 nm. The conversion did not vary much with pore size for catalysts coded as MM-7
to MM-12. The gaseous product remained almost constant at about 10 wt.%, whereas the
coke formation increased with decreasing pore size. The catalysts (MM-1 to MM-6) used
for the cracking of palm kernel oil gave highest kerosene yield among the liquid products
and kerosene content was increased with the increase of pore size. The gasoline yield was
also increased with APS but the opposite trend was observed for diesel yield. However,
when palm olein oil was cracked over the same set of catalysts, diesel yield was highest
and it decreased with the increase in pore size and gasoline yield decreased with the
Fig. 9. Effect of the surface area of mesoporous aluminosilicate catalyst on the selectivity of total products from
cracking of palm oil olein (a) prepared using C
12
TMA (b) prepared using C
16
TMA.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 117
increase in the diesel production. The kerosene yield was low and remained almost
constant. Fig. 7a and b shows the effect of surface area for (MM-1 to MM-6) catalysts on
the selectivity of products for palm kernel oil cracking. It was observed that the selectivity
of gaseous products and coke were almost constant, whereas the selectivity for OLP was
decreased with the change of surface area of the catalyst.
The effect of the pore size was pronounced at medium pore size distribution, which was
closer to the size of the triglyceride molecule. The effect of pore size at large pore
openings diminished because the reactant could diffuse in the pores easily. The selectivity
for liquid products such as gasoline, kerosene and diesel from palm kernel oil and palm
olein oil are presented in Fig. 8a and b, respectively. The selectivity was found
independent with the change of surface area as well as average pore size (APS) of the
catalyst. Many factors were responsible for the cracking reaction beside surface area of the
catalysts. The crystallinity of the prepared material could also affect cracking activity.
MM-1 to MM-12 mesoporous MCM-41 materials have different crystalline order and
therefore gave different cracking activities.
Fig. 10. Effect of the surface area of mesoporous aluminosilicate catalyst on the selectivity of liquid products from
cracking of palm oil olein (a) prepared using C
12
TMA (b) prepared using C
16
TMA.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 118
Fig. 9a and b shows the selectivity of products from catalytic cracking of palm
olien oil over both sets of catalysts MM-1 to MM-6 and MM-7 to MM-12, res-
pectively. The selectivity of gaseous products was increased with pore size in the range
of 1.82.2 nm, and selectivity for OLP was decreased with the increase of average
pore size. The selectivity for gaseous products and OLP were remained constant with
pore size when the palm olein was cracked over catalysts having pore size in the range
of 2.32.8 nm.
When the catalysts (MM-7 to MM-12) were used, a linear drop in the conversion
against pore size was observed. The gaseous product was almost constant and coke
formation was decreased. When palm kernel oil was fed to the reactor, the gasoline
and kerosene yields were almost equal and increased with increase in pore size. The
diesel yield was dropped from 25 to 12 wt.% as the pore size increased from 2.3 to
2.8 nm.
The highest gasoline yield was obtained from palm olein oil. The effect of the pore size
on the gasoline selectivity was more pronounced with palm olein oil. As the pore size was
increased, the space available for reactions also increased where the active sites located
inside the pores of MCM-41 catalyst. The selectivity for liquid products gasoline, kerosene
and diesel from palm olein oil is presented in Fig. 10a and b, respectively. The selectivity
of gasoline and kerosene were increased with the increase in surface area of the catalysts
for both sets. The selectivity for diesel was independent with the change of surface area.
The higher surface area gave higher conversion of palm olein oil. Palm olein oil was found
more influenced with the average pore size of the catalyst compared to palm kernel oil,
which has smaller molecular weight. The catalysts prepared using C
16
TMA template gave
higher selectivity for gasoline.
4. Conclusion
The average pore size of (APS) of aluminosilicate mesoporous materials was altered by
replacing C
12
TMA with C
16
TMA template and enhancement in the pore characteristics
was achieved by the addition of ODA. The synthesized MCM-41 gave good catalytic
activities for conversion of palm oil to liquid fuels. The conversion of lower-molecular-
weight palm kernel oil was higher. The selectivity of the catalysts towards a particular
liquid product was found to depend on the type of palm oil used for cracking. The
selectivity for particular liquid hydrocarbons such as gasoline, kerosene or diesel was
dependent on the pore size and the surface area of the catalyst. High coke formation was
observed on the MCM-41 catalysts during cracking reaction.
Acknowledgements
The financial support by the Ministry of Science, Technology and Environment,
Malaysia under long-term IRPA grant (Project: 03-02-05-7005) is gratefully acknowl-
edged. The assistance provided by Dr. Siegfried Hafnec of Varian in Dawnstadt, Germany
for obtaining the NMR spectra of the MCM-41 samples is also acknowledged.
F.A. Twaiq et al. / Fuel Processing Technology 84 (2003) 105120 119
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