Feasibility of Biomass ANTONIO,

MA. DANIELA M.

Briquette Production
from Municipal Waste MALAZARTE,
KRISTINE C.

Streams by Integrating
the Informal Sector in RIVERA,
ANNA R.

the Philippines (2020)

Tanquilut, M.R., Genuino, H., Wilbers, E., et.al
YUZON,
JOHN HAROLD R.
TABLE OF CONTENTS
TABLE OF CONTENTS
TABLE OF CONTENTS
TABLE OF CONTENTS
TABLE OF CONTENTS
1. INTRODUCTION
1. INTRODUCTION
• Biomass is one of the alternative sustainable
resources
• Pyrolysis is the most commonly used
thermochemical conversion for the direct
transformation of these renewable (non-food)
resources to bio-oil, which can be converted to
fuels and chemicals.
• Pigeon pea [Cajanus cajan (L.) Millsp.] wood is a
potentially interesting biomass feed for pyrolysis.
• The International Crop Research Institute in
Semiarid Tropics (ICRISAT) reported that about
15–20 tons ha 1 of fuel wood from pigeon pea
plantations can be obtained, with an energy
density of about 4000 kcal kg^-1.
 1. INTRODUCTION

Integrating pyrolysis technology in a cascading biorefinery

approach for pigeon pea
 1. INTRODUCTION

• The characteristics of pigeon pea wood

residues such as having low lignin content,
proximate, elemental composition, and heating
value could be advantageous for pyrolysis
processes.
• Studies in the use of pigeon pea wood for
pyrolysis to produce bio-oils has not been
reported.
2. EXPERIMENTAL
SECTION
2. EXPERIMENTAL SECTION

2.1. Biomass Preparation and Characterization

• Pigeon pea wood samples were collected from
the pigeon pea plantation area located in the
municipality of Magalang, province of
Pampanga in the Philippines.
• Wood samples are size-reduced, hammer
milled, dried, sieved, analyzed
thermogravimetrically, and heated under a
nitrogen atmosphere.
 2. EXPERIMENTAL SECTION
2.2. Pyrolysis Experiments and Experimental Design
• Pyrolysis experiments were carried out in a semi-continuous setup (continuous with
respect to N2 gas and batch regarding biomass) using gram amounts of biomass
input. A total of fifteen pyrolysis runs were carried out at temperatures between
400 and 600 °C, nitrogen flow rates of 7, 11 and 15 mL min−1 and biomass particle
sizes of 0.5, 0.9 and 1.3 mm. Each pyrolysis experiment was conducted with a
constant flow of N2 gas (Linde Gas, 99.999% purity) for 15 min The pyrolysis
vapor diluted with nitrogen gas was condensed at a temperature of −40 °C (liquid
nitrogen–ethanol mixture). The mass of bio-oil produced (mbo) was determined
from the difference of the weight of the tube linings and condensers before and
after pyrolysis. The bio-oil was collected from the tube linings and condensers by
thoroughly washing them with tetrahydrofuran (THF, Sigma Aldrich, anhydrous,
≥99.9%, with 250 ppm BHT as inhibitor, typically about 3 g). The bio-oil yield was
calculated using Equation:
 2. EXPERIMENTAL SECTION

2.2. Pyrolysis Experiments and Experimental Design

Schematic diagram of the reactor setup for the pyrolysis of pigeon pea wood
 2. EXPERIMENTAL SECTION

2.2. Pyrolysis Experiments and Experimental Design

• A response surface methodology (RSM) was applied to
determine the influence of pyrolysis temperature, particle
size, and N2 flow rate, coded as X1, X2, and X3 (independent
variables), on the bio-oil yield, coded as Y (dependent
variable). A Box-Behnken three-level, the three-factor
fractional factorial design was used (Table 2). Four
combinations of the factor variables and three center points
were included in the design to determine reproducibility.
 2. EXPERIMENTAL SECTION

2.2. Pyrolysis Experiments and Experimental Design

Box-Behnken three-level three-factor fractional factorial design matrix.

 2. EXPERIMENTAL SECTION

2.3. BIO-OIL CHARACTERIZATION

• The water content of bio-oils was measured
using a Karl–Fischer Titrator following the
ASTM E203 standard.
 2. EXPERIMENTAL SECTION
2.3. BIO-OIL CHARACTERIZATION
• Triplicate measurements for each sample were conducted and the average value
is reported. The total acid number, heating value, ash content and elemental
composition of bio-oils (after removal of THF by evaporation) were determined.
The total acid number (TAN) titration was performed following ASTM D 3339–
07 using about 0.25 g of bio-oil. The proximate composition was determined
according to ASTM D5142 on a thermal gravimetric analyzer (TGA 4000) from
Perkin Elmer Instruments. The analyses were carried out from 25 to 950 °C under
an inert nitrogen gas as well as air at a heating rate of 20 °C min−1. The
moisture content was taken as the weight loss between 25 and 110 °C. The ash
content was taken as the amount of residue when heating a sample in air until
950 °C. The fixed carbon content (%) was taken as 100% minus the amount of
volatile matter (%) and ash content (%). The elemental composition of the bio-
oils was determined using an elemental analyzer (Vario Micro Cube Elemental
CHNS/O, Germany). The oxygen content was determined by difference. All
experiments were carried out in duplicate, and the average value is provided.
3. RESULTS AND
DISCUSSION
 3. RESULTS AND DISCUSSION
3.1. DESCRIPTION OF A TYPICAL EXPERIMENT

Proximate and ultimate analyses, as well as relevant physicochemical properties of the pigeon
pea wood used for pyrolysis were compiled from the literature and are reported in Table 1.
 3. RESULTS AND DISCUSSION

3.1. DESCRIPTION OF A TYPICAL EXPERIMENT

• Pigeon pea wood was pyrolyzed in a small-scale setup using
1.0 g biomass sample. Benchmark pyrolysis experiments were
initially performed at a temperature of 500 °C and a
nitrogen flow rate of 11 mL min−1 using 0.9 mm particle size
(3 trials). After the reaction, 46 wt.% ± 1.1 wt.% (relative to dry
biomass intake) of a condensed product (two phases in the
condenser, a dark brown heavy oil phase, and a separate
water phase) was obtained.
 3. RESULTS AND DISCUSSION

3.2. Optimization Studies

• The pyrolysis process was subsequently optimized and
validated. Measurements were performed at least in
duplicate and the average yields are provided. Good
reproducibility (and mass balance closures were achieved in
all the runs.
• Fifteen pyrolysis experiments were performed following the
RSM method or the Response surface methodology to
determine the effects of temperature, particle size of pigeon
pea wood and N2 flow rate on the yield of bio-oil.
 3. RESULTS AND DISCUSSION
3.2. Optimization Studies
 3. RESULTS AND DISCUSSION

3.2. Optimization Studies

• Figure 3 presents a parity plot of the experimental bio-oil
yields versus the model predictions. It clearly reveals that the
model yields are in good agreement with the experimental
ones. The R2 value (0.9646), in combination with high values
for the predicted and the adjusted R2 , suggest that the
model represent the dataset well.
 3. RESULTS AND DISCUSSION
3.2. Optimization Studies
 3. RESULTS AND DISCUSSION

3.2. Optimization Studies

• Figure 4 shows the interactive effects of particle size and N2
flow rates on bio-oil yield at two temperatures (400 ◦C, left
and 466 ◦C, right). The following observations can be drawn:
(1) bio-oil yields are considerably reduced at intermediate N2
flow rates, whereas the effect of temperature is less
pronounced within the temperature window explored, and (2)
bio-oil yields are surprisingly highest when using larger
particle sizes.
 3. RESULTS AND DISCUSSION
3.2. Optimization Studies
 3. RESULTS AND DISCUSSION

3.3. Validation of Optimized Model Conditions and Comparison

of Bio-Oil Yields Obtained in a Fluidized Bed Reactor
• With the model available, the optimum pyrolysis temperature,
biomass particle size, and N2 flow rate regarding bio-oil yield can
be determined. The highest bio-oil yield predicted by the model was
54 wt.% at a temperature of 466 ◦C, a biomass particle size of 1.3
mm, and a nitrogen flow rate of 14 mL min−1 .
• To verify the accuracy of the model, three validation experiments
were performed at these optimum conditions. A preliminary scale-up
experiment using a fluidized bed pyrolysis reactor at a scale of 100
g h−1 input was also performed. As such, further experiments will be
required in this setup to optimize the oil yields and these will be
performed in subsequent studies.
 3. RESULTS AND DISCUSSION

3.4. Properties and Molecular Composition of the Bio-Oils

• With the model available, the optimum pyrolysis temperature,
biomass particle size and N2 flow rate regarding bio-oil yield
can be determined. The highest bio-oil yield predicted by the
model was 54 wt.% at a temperature of 466 ◦C, a biomass
particle size of 1.3 mm and a nitrogen flow rate of 14 mL
min−1 .
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils
 3. RESULTS AND DISCUSSION

3.4. Properties and Molecular Composition of the Bio-Oils

• In Figure 5, the values for wood and bio-oils derived from
wood, as well as the value for crude oil, are displayed. By
considering the biomass feeds, it is obvious that the O/C and
H/C values of pigeon pea wood are greater than those of
"typical" wood.
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils
• Figure 6 presents the GPC chromatogram for the bio-oil
obtained from pigeon pea wood pyrolysis at optimized
conditions. It shows a number of sharp strong peaks in the low
molecular weight region (i.e., between ~100 and 200 g mol−1),
an indication for the presence of considerable quantities of
low molecular weight products, in line with the GC-data.
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils

Figure 7 depicts the 13C-NMR spectrum of the bio-oil derived from pigeon pea wood, which
reveals multiple peaks of various functional groups.
 3. RESULTS AND DISCUSSION
3.4. Properties and Molecular Composition of the Bio-Oils

Figure 8 depicts the 2D HSQC-NMR spectrum obtained for the bio-oil derived from pigeon
pea wood. Many significant locations have been allocated to different C-H bonds
4. CONCLUSIONS
 4. CONCLUSIONS
• An experimental study was performed on the pyrolysis of pigeon
pea wood, a local and widely available biomass resource in the
Philippines. Results showed that the highest bio-oil yield attained
was 54 wt.% on dry feed intake. Validation experiments indicated
good agreement between the average experimental (52 wt%) and
predicted bio-oil yields.
• Characterization of the bio-oil revealed that it has a low ash
content and a heating value considerably higher than the feed.
GC–MS analysis showed that it contains a vast range of functional
groups of aliphatic, aromatic, aldehydes, ketones, carboxylic acids,
phenolics, and oligomeric products.
• This work is expected to contribute to the development of efficient
biorefining concepts for pigeon pea and may have a positive effect
on local development and economies.
 THANK YOU
ANTONIO, MALAZARTE, RIVERA, YUZON,
MA. DANIELA M. KRISTINE C. ANNA R. JOHN HAROLD R.