Catalyst support Biomass Reaction parameters Maximum Deactivation Advantages

conversion
Vegetable Waste vegetable Time (4.5hr) Triglyceride(80.5 The high catalytic activity and
oil asphalt oil(rapeseed, Temperature (220) wt.%) stability of this catalyst was related to
cottonseed and Methanol:oil (16:8) FFA (94.8 wt.%) its high acid site density (OH,
soybean Catalyst to oil (0.2 wt.%) Bronsted acid sites), hydrophobicity
acidified oils) that prevented the hydration of OH
species, hydrophilic functional groups
(SO3H) that gave improved
accessibility of methanol to the
triglyceride and FFAs, and large pores
that provided more acid sites for
the reactants.
Calcium oxide Waste cooking Time (8hr) FAME (94%) Its high specific surface area, inert
supported on palm oil (WCO) Temperature (60) carbon skeleton and controllable pore
palm shell Methanol:oil ratio (25:1) structure allow catalyst to disperse
activated over it largely and effectively. It is
carbon stable in high pressure and
(CaO/AC) temperature reaction condition
a) Biochar Vegetable oil and Time (30-60min) 90100% Drying the biochar H2SO4 sulfonation of the biochar
(pyrolysis) animal fat Temperature (55-60) catalysts for 1 h at 125 clearly increased surface area and
Methanol:oil ratio (25:1) C between pore structure of the biochars, yet did
uses maintained not generate acid densities as high as
esterification activity, SO3 sulfonation.
allowing the catalysts
to be reused up to 7
cycles.
b) wood based For the SO3 Wood based activated carbon
activated sulfonated sulfonated using SO3 generated a
carbon Wood based AC solid acid catalyst with the highest
catalyst, such a esterification activity and reuse
regeneration step was capability due to a combination of
not required, as the particle strength, hydrophobicity
fractional conversion (difference between total acid density
of palmitic and SO3H group density), and high
and stearic acid (5% surface area (1137 m2/g) and sulfonic
FFA, 10:1, 3 h) acid group density (0.81 mmol/g).
remained >90% after 6
cycles.
K2CO3 Rapeseed oil Time (2hr) FAME (99.6%) The solid catalyst can Simple preparation method,
supported Kraft Temperature (65) be reused for 4 times environmentally friendly, low-cost,
lignin activated Methanol:oil (15:1) and biodiesel yield high catalytic efficiency and
carbon Catalyst to oil (3 wt.%) remained over 82.1% reusability
(K2CO3/KLC) for the fourth time.
(one-step in
situ)
potassium Palm oil Temperature (64.1) FAME (98.03%) It was found that
hydroxide catalyst Methanol:oil (24:1) conversion unalterability
supported on palm Catalyst to oil (30.3 wt.%) of the three time used
shell activated catalyst is reasonably
carbon good. The catalytic
activity remains 90.6% of
the fresh catalyst when
the activated carbon
supported catalyst is
employed for the third
time.
Activated Palm stearin Time (4hr) Ca(NO3)2/AC The supported alkali earth metal
Carbon from Temperature (60) (98.5%) catalysts, Ca(NO3)2/AC showed
Palm Shell Methanol:oil (20:1) CaO/AC (95.3%) almost the same
Ca(NO3)2/AC to oil (10.5 activity under the optimized
wt.%) reaction conditions compared to
calcium oxide catalyst (CaO).
CaO/AC to oil (6 wt.%)
Due to higher surface area of
CaO catalyst which results in an
activation of active sites
of the catalyst, as low as 6 wt.%
in the amount of CaO catalyst
was required to produce the
biodiesel with the comparable
methyl ester content as in
Ca(NO3)2/AC catalyst. Using the
catalyst amount of
12 wt.% can improve the methyl
ester content to 100%.
Additional explaination

Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a
carbon-based solid acid catalyst
Qing Shu, Jixian Gao, Zeeshan Nawaz, Yuhui Liao, Dezheng Wang, Jinfu Wang*

1) Catalyst preparation
The carbon carrier was obtained by carbonizing vegetable oil asphalt.
1. The vegetable oil asphalt from a biodiesel plant was pre-treated to remove water and residual esters.
2. Batches of 10.0 g of extracted vegetable oil asphalt were oxidized for 1.0 h at 280 C in a stream of
air (300 mL/ min).
3. These were heated to 500700 C at a rate of 2 C/ min under an argon atmosphere (300 mL/min).

Sulphonation of carbon carrier:

1. Carbonized vegetable oil asphalt (5.0 g) and 100 mL concentrated H2SO4 (96%) solution were put
into a 250 mL flask controlled at 210 C in an oil bath. This was kept under reflux and agitation for
10.0 h.
2. After the treatment, the suspension was washed with distilled water and dried at 120 C under
vacuum for 4 h to obtain the sulfonated vegetable oil asphalt catalyst.

2. Characterization of catalyst

Scanning electron microscopy (SEM), powder X- structure of vegetable oil asphalt-based solid acid
ray diffraction (XRD), X-ray photoelectron catalyst
spectroscopy (XPS) and Raman spectroscopy

Temperature programmed amount of acid in the catalysts

desorption (TPD) of NH3
Elemental analysis using EDS sulfur contents of the sulfonated carbon catalysts

Acidbase titration method total acid site concentrations of the catalyst

N2 adsorptiondesorption BET surface area and pore size

BarrettJoynerHallenda (BJH) pore size analysis pore size distribution of the catalysts

Structure of vegetable oil asphalt-based solid acid catalyst

The carbonized vegetable oil asphalt exhibited a loose irregular network structure, and several pores
with sizes of lm can be found. The pores became larger when the obtained carbon precursor was
treated by concentrated H2SO4. This is because straight chain aliphatic hydrocarbon polymers can
more easily form pores than ring hydrocarbon polymers when they were incomplete carbonized. The
larger amounts of pores and larger
pore size would increase the accessibility of sulfuric acid into the carbon powder bulk, which would
give a higher concentration of covalently bonded carbon with an SO3H group. The incorporation of a
larger amount of hydrophilic functional groups (SO3H) into the carbon sheet will improve the
hydrophilicity of the carbon material, such that hydrophilic methanol molecules also can more easily
get into the interior of carbon bulk and react with the hydrophobic reactants (FFA and triglyceride) on
the interior
acid sites of this catalyst.

Porosity
Since the prepared vegetable oil asphalt catalyst is a porous material, so it maybe expected to
show a superior catalytic activity

XRD pattern
XRD pattern indicated that this sample comprised a high content of non-graphitic carbon..

Raman spectrum
The G band is commonly observed in graphitic materials while D band is commonly associated with
the presence of defects in the graphite layer.The ratio of the relative intensities of the D band to G
band is a measure of the degree of structural order. The relative intensity ratio of the D/G bands for
this asphalt catalyst was 0.94. The asphalt catalyst can be deduced to have more defects than the
cellulose catalyst since the difference in the D/G intensity ratios can be attributed to the change in
surface functionalities (or local defects) resulting from breaking CC bonds in the carbon material.
This more defective surface would have resulted from the C-C cleavage and the formation of carboxyl
and hydroxide group. The CC bond breaking also can help the
non-graphitic carbon to couple with the SO3H group to form a stable covalent structure, such that
this catalyst can maintain good stability at the high reaction temperature.

NH3-TPD
There is two distinct desorption peaks from 250 to 300 C and 500 to 700 C that were assigned to two
types of acid sites.The low and high temperature peaks corresponded to weak and strong acid sites,
respectively. A broad desorption peak appeared at 500 700 C, which was due to the strong acid
sites.The appearance of weak and strong acidity can be ascribed to the influences of the size of the
pore and the position of acid site. Roughly
speaking, the weak acidity is primarily related to interactions among ammonia molecules in the pores,
whereas the strong acidity is primarily related to interactions between the NH3 molecules and the pore
walls of the catalyst.

EDS result
The EDS results showed that the contents of sulfur was 7.07 wt.%.

Sulfur analysis
Based on sulfur analysis, the acid site density was 2.21 mmol g1, and the sites were Bronsted acid
sites. The titration of acidic groups showed that the acid site density is 2.04 mmol g1. The high acid
site density can be due to the following: the presence of many pores and the large pore size will
increase the accessibility of sulfuric acid into the carbon powder bulk, and the high concentration of
non-graphitic carbon on it helped to form more covalent bonds with the SO3H groups to give a
higher concentration of covalent bonds (carbon with SO3H group). This catalyst would be expected
to have a higher activity for the production of biodiesel from waste oil with a high content of FFA
because it has more acid sites and stronger acidity.

BET surface area

The average pore size of this catalyst was 43.90 nm and the BET surface area was 7.48 m2 g1. The
low surface
area and high SO3H density indicated that most of the SO3H groups of this catalyst were in the
interior of the powder.Since the average pore size of the sulfonated vegetable oil asphalt was 43.90
nm, which was large, reactant can easily diffuse into the interior of the catalyst powder. This allowed
reactants to contact
with more acid sites, and the catalyst would have better activity.
XPS
According to XPS analysis, all sulfur in the carbon material is expected to be confined to SO3H
groups. These results from SEM, XRD, Raman, TGA, XPS and NH3-TPD clearly indicated that the
VC-600S-210 catalyst would be a catalyst with good thermal stability and high activity.

Conclusion
This solid acid consisted of a flexible carbon based framework with highly dispersed polycyclic
aromatic hydrocarbons containing sulfonic acid groups. The high activity can be ascribed to the high
acid site density, the hydrophobicity of its carbon sheet that prevented the hydration of OH, and the
bonded hydrophilic functional groups (SO3H) that allowed more methanol to contact the protonated
carboxylic/carbonyl group of the reactants (FFA and triglyceride). The conversions of triglyceride and
FFA were 80.5 wt.% and 94.8 wt.%, respectively, when the methanol/oil molar ratio was 16:8,
reaction temperature was 220 C, reaction time was 4.5 h and catalyst/mixed oil mass ratio was
0.2%.The prepared vegetable oil asphalt-based solid acid catalyst can be easily separated from the
product by filtration, which avoids the washing requirement.

Biodiesel production from waste cooking palm oil using calcium oxide supported on activated
carbon as catalyst in a fixed bed reactor
Achanai Buasri*,**,, Bussarin Ksapabutr*,**, Manop Panapoy*,**, and Nattawut Chaiyut*,**

1. Catalyst Preparation
Supported metal oxide catalysts were prepared according to the conventional incipient-wetness
impregnation of aqueous solutions of the corresponding Ca(NO3)24H2O precursors on an activated
carbon support. Calcium nitrate salt was completely dissolved in deionized water at room temperature.
Amount of metal loading was maintained at 20mmol metal/g support. The support was then added into
the solution followed by vigorous mixing. After mixing for 4 h, the paste was dried in an oven at 120
oC overnight. The dried solid was calcined at 600 oC for 4 h. The characterization of these
synthesized catalysts has been reported in our previous publication.
In situ preparation of K2CO3 supported Kraft lignin activated carbon
as solid base catalyst for biodiesel production
Xian-fa Li a,b, Yong Zuo a, Ying Zhang a, Yao Fu a,, Qing-xiang Guo a,

1. Catalyst Preparation
K2CO3 was physically mixed with KL according to various K2CO3/KL mass ratios. The
K2CO3/KLC catalysts were obtained from K2CO3/KL mixture after being activated at 500900 C for
2 h with the heating rate of 10 C/min under the N2 flow (100 cm3/min) in a tubular furnace made of
stainless steel. The prepared K2CO3/KLC catalysts were ground and stored in desiccator to reserve.

2. Catalyst Characterization
VARIO ELIII (Germany) instrument
Thermobalance (DTA-50, Shimadzu)
Bruker Equinox 55 spectrometer
SEM (Model JSM-6700F, JEOL) and
XRD (Philips XPert PRO SUPER, 2 kW)
N2 adsorptiondesorption isotherms
Brunauer, Emmett, Teller (BET) method
N2 adsorption isotherm
Barrett, Joyner and Halenda (BJH)
method
X-ray photoelectron spectroscopy (XPS; model:
ESCALAB 250, Thermo-VG Scientific)
analysis of C, H, S and N content in KL
weight loss behavior of KL, K2CO3 and K2CO3
supported on
KL during the activation
Fourier-transform infrared (FTIR) spectra
surface morphologies and physical structure of
the support and catalysts
surface area, pore volume and pore diameter of
KLC supports and catalysts
specific surface area
Total pore volume
calculation of the average pore diameter
potassium content of the catalysts

Characterization results
KL has high carbon and low ash content, which is a good starting material for the preparation of
KLC. The sulfur content is 0.9%. After activation, the sulfur content of catalyst had decreased to
as low as 0.2% (not shown), which is desirable to avoid the contamination of sulfur in the
biodiesel product.
The FTIR analysis of K2CO3 and the catalysts shows that carbonate had been partially
decomposed at 900 C. This result is also confirmed by TGA and DTA results.
 XRD pattern of unactivated 0.6 K2CO3/KL is similar to that of bulk K2CO3, whereas the XRD
pattern of 0.6 K2CO3/KL activated at 800 C clearly shows that the diffraction peak of K2CO3
nearly disappears compared to that of 0.6 K2CO3/KL. However, according to the results of TGA
and DTA, K2CO3 do not decompose obviously at 800 C. The possible reason for the
disappearance of K2CO3 diffraction peak is that most of the K2CO3 particles filled or dispersed
in the KLC support pores (Fig. 3B) would be too small to create a diffraction pattern.
It could be noticed that the surface area and the pores volume increased rapidly with the
activation temperature increasing.Interestingly, the surface area of catalysts increased sharply
from about 41 m2/g to 440m2/g with increasing the activation temperature from 800 C to 900 C.
The possible reason is that at 800 C the non-porous K2CO3 (without decomposition) was filled
(or retained) in porous carbon leading to relatively low surface area. When the activation
temperature increased to 900 C,the intercalated K2CO3 decomposed rapidly and the blocked
pores (micropores and mesopores) were opened. So, the surface area of catalyst increased
obviously.
To further understand the correlation of the surface area and K2CO3 content under different
activation temperatures, the catalysts were washed several times with deionized water to remove
K2CO3 and dried at 105 C to prepare KLC supports. It was deduced that K2CO3 was effective
and stable as activation reagent at around 800 C. This result also supported that K2CO3 was
reduced by carbon at above 800 C and then was removed during gasification.
The SEM image (Fig. 3A) shows that 0.6K2CO3/KLC catalyst activated at 800 C had smooth,
flower like morphology without any pores on the surface. K2CO3 particles highly dispersed in
the structure of KLC support are nearly undistinguished with KLC particles.

3) Stability and recycling of catalyst

The biodiesel yield decreased slightly after four runs and the catalyst could be repeatedly used four
times with biodiesel yield over 82.1%. The decrease of catalytic activity after the fourth recycling was
caused by two main reasons. One of the reasons may be due to the loss of catalyst during the process
of centrifugation, activation and recovery. The other reason may be the morphology change of used
catalyst. The particles aggregation of catalyst after the third time used can be observed which could be
associated with its reduced catalytic activity. The leaching of potassium species into biodiesel phase
after first run was determined using ICPOES. The leaching of potassium species was only 4.2 mg/kg
of biodiesel, which can satisfy the EN 14214 standards (below 5.0 mg/kg of biodiesel).

4. Conclusion
The K2CO3/KLC catalysts, which were prepared one-step in situ by mixing of K2CO3 with various
mass ratio of powdery KL followed by activation at different temperature under N2 flow,showed high
catalytic activities for the transesterification reaction. The experimental results show that optimal solid
catalyst preparation condition is 0.6 of K2CO3 to KL mass ratio and 800 C of activation temperature
for 2 h. When optimal catalyst was used in the transesterification of rapeseed oil to biodiesel, the
highest biodiesel yield reached 99.6% under the optimal conditions as catalyst amount of 3.0 wt.%,
methanol to oil molar ratio of 15:1, reaction time of 2 h and reaction temperature of 65 C. The catalyst
could be recycled and reused four times without remarkable deactivation. The prepared K2CO3/KLC
solid base catalyst has features of simple preparation method, environmentally friendly, low-cost, high
catalytic efficiency and reusability, and can be regarded as a promising heterogeneous base catalyst
candidate for the large scale biodiesel production.

Potassium hydroxide catalyst supported on palm shell activated carbon for transesterification of
palm oil
Saeid Baroutian, Mohamed Kheireddine Aroua , Abdul Aziz Abdul Raman, Nik Meriam Nik Sulaiman

1) Catalyst preparation
A potassium containing solution was prepared by dissolving KOH in deionized water. Activated
carbon was sieved to size range from 550 to 810 m, washed with deionized water to remove fines
and dirt,
oven dried at 110 C for a day, cooled in a desiccator and stored in glass containers. Activated carbon
was divided in 10 g portions and placed in separate Erlenmeyer flasks and 150 ml of potassium
hydroxide solution with initial concentration of either 0.025 to 0.500 g/ml was added. Activated
carbon together with the KOH solutions was then agitated in an orbital shaker at 180 rpm at constant
temperature of 25 C for 24 h. The amount of adsorbed KOH was measured by gravimetrical method.
The total loading content of the potassium salts was 5.645.9% by weight based on the weight of
activated carbon.

2) Catalyst characterization
D8 Advance X-Ray XRD measurements
Diffractometer-Bruker AXS
EI Scanning electron micrographs (SEM)
Quanta 200 FESEM scanning electron
microscope
Adsorption of nitrogen specific surface area and pore volumes

The SEM photographs of virgin activated carbon and potassium hydroxide supported catalyst on
activated carbon (KOH/AC) showed a good dispersion of potassium hydroxide on the surface of
activated carbon. Based on these results, after loading of potassium hydroxide, activated carbon
retained its structure that was important for catalysis and therefore the potassium species was
found highly distributed upon the surface of the support.
The significant reduction in BET surface area from virgin activated carbon (1015 m2/g) to the
KOH/AC catalyst (214.46 m2/g) indicates filling of potassium hydroxide molecules into the
activated carbon pores and confirmed the results of previous textural characterizations.

3) Catalyst reusability
It was found that conversion unalterability of the three time used catalyst is reasonably good. The
catalytic activity remains 90.6% of the fresh catalyst when the activated carbon supported catalyst is
employed for
the third time. This decay could be due to the leaching of active sites to the reaction media. Not with
standing the interaction between the potassium species and activated carbon surface, the supported
species are leached by the reaction media. Leaching of the active phase to the alcoholic phase can be
attributed to the bond breaking and formation of K+ and CH3O. The KOH/AC catalyst exhibits a
favorable reusable performance during the transesterification reaction.

4. Conclusion
The potassium hydroxide catalyst supported on palm shell activated carbon used in this work showed
high performance to produce biodiesel from palm oil. The response surface methodology based on
central composite design was employed to optimize the production of palm biodiesel. Among the
transesterification parameters, reaction temperature and catalyst loading were found to bemost the
significant parameter on production yield and catalyst leaching, respectively. The optimum condition
of transesterification using activated carbon supported catalyst was 64.1 C reaction temperature, 30.3
wt.% catalyst loading and 24:1 methanol to oil molar ratio. Under these optimum conditions 98.03%
production yield was obtained with catalyst leaching of 0.53 ppm. The produced biodiesel under the
optimum conditions was characterized and its chemical/physical properties were within the ASTM
standard.
Preparing Activated Carbon from Palm Shell for Biodiesel Fuel Production
Achanai Buasri*[a,b], Nattawut Chaiyut [a,b] and Chaiwut Nakweang

1) Catalyst Preparation

Supported metal oxide catalysts were prepared according to the conventional incipient-wetness
impregnation of aqueous solutions of the corresponding Ca(NO3)2 .4H2O (AR grade, Ajax
Finechem) precursors on an activated carbon support (100 mesh particle size, Darco). Calcium nitrate
salt was completely dissolved in deionized water at room temperature. Various amount of metal
loading was maintained at 10, 15 and 20 mmol metal/g support. The support was then added into the
solution followed by vigorous mixing. After mixture for 4 h, the paste was dried in an oven at 120oC
overnight. The dried solid was calcined at 450oC for 4 h.

Calcium oxide (CaO) used in the transesterification process was obtained from the calcination of
precipitated calcium carbonate puriss, Sigma-Aldrich) at 800-900oC for 1.5 to 4.5 h in muffle furnace.

2) Characterization
Surface area analyzer (Quantachrome,
Autosorb-1MP)
X-ray diffractometer (JEOL,JDX-3530, 2kW)
Scanning electron microscope (JSM-5800LV)
BET surface area, total pore volume
and average pore diameter
structural of metal oxide catalysts
Morphological study

The BET surface areas and the total pore volumes of activated carbon decreased with loading
calcium nitrate, and less than in the case of calcium oxide. The surface area of activated carbon
increases with increasing impregnation ratio from 0.5 to 1.0 and decreased slightly for ratios
larger than 1. However, mesoporous surface area increased continually. There was a pronounced
decrease in micropore surface area when the ratio was higher than 1 due to enlargement of
 micropores to mesopores. These results suggested that to obtain the optimal value of surface area,
the impregnation ratio should be around 1.0.

According to the TGA patterns of activated carbon, calcium carbonate, non-calcined

Ca(NO3)2/AC and calcined Ca(NO3)2/AC. It was found that Ca(NO3)2 in non-calcined
Ca(NO3)2/AC was completely decomposed to CaO at about 450oC. On the other hand, calcined
Ca(NO3)2/AC exhibited one-step decomposition of activated carbon (38% weight loss) at
650oC, while pure activated carbon showed weight loss of around 87% from decomposition at
600oC. The results indicated that the catalysts contained metal more than 50 wt.% and the
calcium carbonate was completely decomposed to CaO at temperature about 800oC.

Figure 2 compares XRD patterns of Ca(NO3)2/AC catalysts with various amounts of metal
loading in activated carbon after the calcination at 450oC. The several diffraction patterns
corresponding to CaO phase remained concomitantly with the presence of weak peaks related to
nitrate salts when amount of metal loading was maintained at 10 mmol metal/g support (Figure
2a). At 20 mmol metal/g support, the amount of nitrate salts was greatly increased with an
increase in the CaO peaks . Since the calcinations time and temperature largely affect the
structural and catalytic properties of the resultant catalysts, we treated the impregnated catalyst
samples at various times and temperatures to attempt to optimize this.

The XRD diffraction patterns correspond to CaO phase with the presence of CaCO3 phase when
the calcination was performed at 800oC for 1.5 h (Figure 3b). At 800oC for 4.5 h, the amount of
CaCO3 was greatly reduced with an increase in the CaO peaks due to calcium carbonate
decomposition at temperatures above 800oC, as observed in the TGA results (Figure 1). As a
result, no peaks of CaCO3 were found when the calcination temperature above 800oC for 4.5 h.

SEM images shows that the metal loading of 10 mmol metal/g support affected the partial metal
coverage on activated carbon surface. When metal loading increased, activated carbon was
covered with metal almost all the surface (Figure 4c), increasing the active sites. The photographs
of calcium nitrate supported catalyst on activated carbon (Ca(NO3)2/AC) showed a good
dispersion of calcium nitrate on the surface of activated carbon. Based on these results, after
loading of calcium nitrate,activated carbon retained its structure that was important for catalysis
and therefore the calcium species was found highly distributed upon the surface of the support .

CONCLUSION
Transesterification of palm sterain was studied using various catalyst types to producethe biodiesel
with high methyl ester content under different conditions. It was found that Ca(NO3)2/AC yielded
high methyl ester contents (>95%) when the calcination was performed at 450oC and amount of metal
loading was maintained at 20 mmol metal/g support. In addition, the activity of CaCO3 catalysts was
remarkably improved when the calcination was at 800oC for 4.5 h. The suitable conditions for the
transesterification of palm sterain with methanol over Ca(NO3)2/AC and CaO catalyst are the
methanol/oil ratio 20, temperature 60oC, reaction time 4 h, and the appropriate catalyst amount 10.5
wt.% and 6 wt.% for Ca(NO3)2/AC and CaO catalyst, respectively.