FROM BIOMASS TO BIOFUEL

Maisari Utami
Chemistry Department, Universitas Islam Indonesia
OUTLINE

Chlorella vulgaris for Waste Cooking Oil Other Related Works

Biodiesel production into Biogasoline
SIMULTANEOUS EXTRACTION AND IN-SITU TRANSESTERIFICATION OF CHLORELLA
VULGARIS USING MICROWAVE-ASSISTED METHOD FOR BIODIESEL PRODUCTION
INTRODUCTION

• Biomass, the energy source to produce biodiesel, can be classified into three generations.
• The first generation is based on food crops, while the second is from nonfood crops. However, these two
generations have weaknesses, among which they lead to competition for food needs, extensive land
requirement, forest areas reduction and soil pollution.
• The third generation is considered to be more beneficial because it is derived from the use of possible aquatic
biodiversity micro-organisms, namely microalgae.
• Biomass contains a large quantity of oil, usually 20-50% of its weight, and has a fast growth rate. In addition, the
land use is environmentally friendly and effective.
• However, the release of oil from microalgae cells is blocked by rigid cell structures.
INTRODUCTION

 Microwave-assisted extraction may be an option due to its ability to

penetrate the structure of the cell and efficiently remove lipids.
 When microalgae cells are exposed to a microwave frequency (around
2,450 MHz), cell molecules will produce rapid oscillations in electrical
fields, resulting in the production of heat due to the frictional force of inter
and intramolecular motion.
 The interaction between triglycerides, solvent, and microwave leads to a
substantial reduction in activation energy.
 This approach illustrates the advantages of using the microwave, i.e., short
reaction times, low operating costs, and effective extraction.
 INTRODUCTION

• The microwave oven reactor was modified by a reflux system to

maximize the reaction process.
• The condenser causes the solvent to evaporate when it reaches
its boiling point temperature so that it becomes condensed, and
the solvent reacts again.
• Therefore, the solvent quantity remains, and the maximum
reaction occurs without a shortage of solvent to produce the
maximum product.
INTRODUCTION

 In an in-situ transesterification reaction, methanol was used as a solvent due to its high
dissipation factor.
 It gives low ability to block microwave and high ability to dissipate the microwave into
heat.
 However, in-situ transesterification converts triglycerides directly from microalgae to
methyl esters, and since methanol acts as lipid extraction solvent and transesterification
reagent.
 The use of a homogenous catalyst can produce high conversions of biodiesel due to its
susceptibility properties to microwave irradiation.
METHODS

C. vulgaris

KOH + CH3OH Product

Sample preparation Microwave irradiation Chemical characterization

Biomass-to- Catalyst
concentration
Reaction time FTIR GC-MS
methanol ratios (1:6, (20, 30, 40, 50 min) 1H-NMR
1:9, 1:12, 1:15 g/mL) (1, 2, 3 %) SEM
EFFECT OF VARIOUS BIOMASS-TO-METHANOL RATIOS

 The results confirm that the optimum biomass-to-methanol ratio

of 1:12 (g/mL) produced the highest yield of FAME.
 With a limited amount of methanol, it only served to extract lipids
from the cell, while the remaining reacted with triglycerides to
form a small amount of FAME.
 However, a high amount of methanol can cause too much
microwave irradiation to be absorbed by the solvent, leading to
inefficient extraction of lipids from microalgae.
EFFECT OF VARIOUS REACTION TIME

 A reaction time for 40 min produced the highest amount of

FAME.
 A more prolonged reaction time led to a longer reactant
exposed to irradiation from the microwave.
 The thermal effect from microwave enhances the ability of
methanol to extract the lipids from suspended microalgae
biomass.
 However, an excessive reaction time significantly increased the
reaction heat, thus causing solvent removal and by-product
formation.
EFFECT OF VARIOUS CATALYST CONCENTRATION

 It shows that the use of catalyst concentration of 2 wt%

produced the highest amount of FAME.
 However, a lower catalyst concentration was not able to
increase the reactions effectively.
 This maybe due to the presence of various organic compounds
from the extraction of microalgae biomass, such as lipids,
olefins, fatty alcohols, phytols, sterols, and pigments.
FTIR CHARACTERIZATION

 Peaks at 2,924 and 2,854 cm−1 are corresponded to symmetric

and asymmetric stretching vibrations of C–H, respectively.
These vibrations confirm the presence of lipid in microalgae.
 The peak at 2,924 and 2,862 cm−1 are attributed to C–H
vibration in methyl esters.
GC-MS CHARACTERIZATION

 According to GC chromatogram of microwave-assisted in-situ transesterification product at an optimum condition

(biomass-to-methanol ratio of 1:12, reaction time of 40 min and catalyst concentration of 2 %).
1H-NMR CHARACTERIZATION

 The result indicates that the triglyceride was

successfully converted into methyl ester with a total
conversion of 77.64 %.
SEM CHARACTERIZATION

 The surface morphology of microalgae was significantly

changed.
 It indicates that the cell of microalgae had been
damaged by microwave irradiation, then extract lipids
from microalgae to the solvent, and followed by lipid
transesterification with the reagent.
CONCLUSIONS

 Microwave-assisted in-situ transesterification of C. vulgaris was successfully conducted with methanol

as a reagent. Biomass-to-methanol ratio of 1:12, reaction time of 40 min, and catalyst concentration of
2 wt% were determined to be the optimum condition to obtain the highest amount of FAME (11 %).
 The transesterification reaction of C. vulgaris produced FAME conversion of 77.64 %.
 Biodiesel consisted of methyl myristate, methyl palmitoleate, methyl palmitate, methyl linoleate,
methyl oleate, methyl arachidonate, and methyl 5,8,11,14,17 eicosapentaenoate.
NICKEL-MODIFIED SULFATED ZIRCONIA CATALYST: SYNTHESIS AND APPLICATION
FOR TRANSFORMING WASTE COOKING OIL INTO BIOGASOLINE VIA
HYDROCRACKING PROCESS
INTRODUCTION

 Biofuel can be produced from various vegetable oils such as waste cooking oil (WCO).
 The development of heterogeneous catalysts for biofuel production has a significant impact due to its
advantage of easy separation, advanced selectivity, and reuse capability.
 Zirconia (ZrO2) is a good material for a catalytic reaction because of its acidity properties, thermal
stability, and ease of modification. Furthermore, ZrO2 has a vacant site on its surface structure that
catalyzes reactions.
 Modification of zirconia structure via sulfation process had increased the catalyst acidity, forming
superacid sulfated zirconia (SO4/ZrO2).
INTRODUCTION

 Despite having high thermal stability, sulfated zirconia catalysts can get deactivated due to carbon
residues forming to cover the active sites (coke formation).
 Thus, it is required for catalyst modification through metal impregnation.
 One of the promising transition metals, that can be used to impregnate the catalyst is, “nickel”.
 Ni metal impregnation increases the hydrogenation activity of a catalyst through homolytic
dissociation of H2 molecules.
METHODS

(NH4)2SO4
NH3 Zr(OH)4

SO4-ZrO2
ZrOCl2·8H2O

Ni(NO3)2
H2

Ni/SO4-ZrO2

SO4-ZrO2
RESULTS

 The characteristic of the S‒O stretching vibration is

observed in the 990-1219cm -1 range.
 The emergence of sulfate absorption is due to the
coordination bond between SO42- and Zr4+ ions formed
during the sulfation process.
 In the FTIR spectra of the SZ catalysts, there is also an
absorption band at the wavenumber 1473cm-1 indicating
the presence of a double bond in S=O.
 Based on the FTIR spectra of Ni/SZ catalyst, the entry of
metal in the catalyst system caused a narrowing of the
sulfate absorption band (990-1219cm -1) and a decrease in
the absorption intensity at 990-1219 and 1627-1632cm-1.
 The attenuation of this absorption was due to the blocking Fig. 2. FTIR spectra of (a) ZrO2, (b) SZ, (c) 1% Ni/SZ, (d) 2% Ni/SZ and
by Ni metal. (e) 3% Ni/SZ catalysts
RESULTS

 Two absorption bands at around 1126cm-1 and 1404cm-1 were

observed in the IR spectra after the ammonia adsorption test.
 The absorption band at 1126 cm-1 indicated the presence of
ammonia gas absorbed at the Lewis acid site, while the
absorption band in the 1404cm-1 range indicated the
ammonia gas adsorbed at the Brønsted acid site.
 The spectra also show an increase in absorption intensity,
showing an increase in Lewis and Brønsted acid sites.

Fig. 3. FTIR spectra of the catalysts after the adsorption of ammonia:

(a) ZrO2, (b) SZ, and (c) 1% Ni/SZ catalysts
RESULTS

 The ZrO2 catalyst had an acidity imparted from its Lewis acid site (Zr4+
ion) and the acidity was increased due to the presence of sulfates.
Table 1. Total acidity of catalysts
 The induction of electrons in S=O bond from the sulfate group
strengthens the hydroxyl group in donating protons and thus increases Catalyst Acidity
the acidity of the catalyst.
(mmol NH3 g-1)
 Moreover, the impregnation of 1% of Ni metal on the SZ catalyst has ZrO2 1.29
significantly increased the catalyst acidity. SZ 7.16
1% Ni/SZ 9.54
 Nickel metal contributed to the Lewis acid sites causing several acid sites 2% Ni/SZ 5.80
on the catalyst surface to increase. 3% Ni/SZ 5.60

 The decrease in acidity at higher Ni concentration is probably because of

nickel aggregation, which can occur on the outer surface and inside the
pores of the catalyst. As a result, nickel will ultimately block the pores of
the catalyst, decreasing the number of acid sites.
RESULTS

 Modification of ZrO2 with sulfate and Ni metal has affected

the crystal phase of ZrO2.
 The sulfation treatment increased the stability of the
tetragonal ZrO2 phase formation while causing ZrO2 to
recrystallize into a tetragonal phase.
 The crystallinity of ZrO2 decreased with the increase of Ni
metal concentration.
 This data indicates that Ni had been successfully
impregnated on the SZ catalyst.

Fig. 4. Diffractogram of (a) ZrO2, (b) SZ, (c) 1% Ni/SZ, (d) 2% Ni/SZ and
(e) 3% Ni/SZ catalysts
RESULTS

a b

 There are changes in catalyst morphologies

where ZrO2 catalysts tended to have a denser
structure, while SZ had a hollow structure.
 In SZ catalyst, the presence of sulfate can
stabilize the tetragonal ZrO2 and slows
agglomeration or sintering so that SZ particles
have a smaller and uniform size.

Fig. 6. SEM images of (a) ZrO2 and (b) SZ catalysts with magnifications of 1000×
(top) and 10,000× (bottom)
RESULTS

a b

 Ni metal was evenly distributed over the entire

surface of the catalyst and did not form an
agglomerated pattern. c d

Fig. 7. SEM images of (a) 1% Ni/SZ catalyst and EDX mapping of (b) Zr; (c) S; and
(d) Ni
RESULTS

 Hydrocracking of waste cooking oil was carried out in a

reactor without the catalyst at a temperature between 400
and 450 °C in order to find the optimum temperature for
catalytic cracking.
 The optimum temperature would later be used to evaluate
the performance of each catalyst in the conversion of waste
cooking oil into liquid products through the hydrocracking
process.
RESULTS

Table 6. Catalyst selectivity based on GC-MS data

 The increase in the acidity of these catalysts is directly proportional to the Selectivity (%)
number of active sites that facilitate the cracking reaction. Catalyst
Gasoline Diesel Organic
 It suggests that the higher the acidity of the catalyst, the cracking of the feed into
the gasoline fraction will be optimum. In the form of non-hydrocarbon organic ZrO2 26.74 3.61 66.91
compounds, the by-products were produced due to the chemical and physical
interactions between the esters contained in the oil. SZ 44.81 4.69 46.16
1% Ni/SZ 70.28 6.20 19.78
CONCLUSIONS

 The SO4/ZrO2 catalyst was successfully synthesized from zirconyl chloride via a hydrothermal
method, followed by sulfation using ammonium sulfate. Further modification of this catalyst was
carried out by employing Ni metal at various concentrations via a wet impregnation method.
 It was found that the loading of sulfate and 1 wt% Ni metal on the catalyst succeeded in increasing
the acidity of the catalyst.
 The impregnation of Ni metal on the SZ catalyst enhanced both the activity and selectivity for
converting waste cooking oil to gasoline fraction.
OTHER RELATED WORKS
OTHER RELATED WORKS (1)

 Chlorella sp. (28-32%)

 Crypthecodinium cohnii (~20%)
 Dunaliella primolecta (~23%)
 Bothryococus braunii (25-75%)
 Nannochloris sp. (20-35%)
 Isochrysis sp. (25-33%)
 Tetraselmis sueica (15-23%)
 Chlorella vulgaris (20-50%)
OTHER RELATED WORKS (2)

 Several experimental studies had been carried out to produce high conversion of biofuel gasoline
yields from palm cooking oil using suitable catalysts.

Catalyst Modification Feedstock Hydrocracking temperature (°C)

Ni-Cu Doped Zirconia Pillared Bentonite Pillarization-impregnation Palm cooking oil 350

Ni-Mo/Zeolite Ion exchange Palm oil 320

Ni/Mo-ZrO2 Pillared Montmorillonite Pillarization-impregnation Palm oil mill effluent 350

(POME)
Ni/Mo-Alumina Ion exchange Waste palm cooking oil 250
(WCO)

This work Wet impregnation Waste palm cooking oil 450

(WCO)
THANK YOU
maisariutami@uii.ac.id