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seeds
are
side
products
of
known
as
Hevea
Study
Location
Owner
Brgy. Ilayang,
Magdalena (Laguna)
Brgy. Layugan,
Pagsanjan (Laguna)
Atty. Ceriaco
Sumaya
Mr. Alex
Pactananan
Mrs. Ernida
Reynoso
Quezon
Size
No. of Rubber
Trees
5-hectare
3, 000
2.5-hectare
2, 500
5-hectare
5, 000
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in
the
Philippines
was
able
to
generate
small
proportion
of
female
fruit
Rubber fruit
Capsule
Seed
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Shell
Kernel
Composition
Oil
Ash
Protein
Carbohydrate
Others
Percent Content
45.63
2.71
22.17
24.21
5.28
Fatty Acids
Palmitic Acid
Carbon Atoms :
Number of Double
Bonds
C16:0
Percent Composition
10.29
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C18:0
C18:1
C18:2
C18:3
8.68
20.07
58.50
0.80
Source: Biodiesel Production from Rubber Seed Oil Using Limestone Based Catalyst by Gimbun
et al. (2012)
Property
Specific gravity
Viscosity at 40 C (mm2/s)
Flash point (C)
Calorific value (MJ/kg)
Acid value (mg KOH/g)
Percentage
0.9
66.2
198.0
37.5
34.0
Source: Overview of Obtaining Alternative Fuels in The Coliquefaction Processes with Biomass
and Coal in Malaysia by Ishak et al., (2015)
To date, the oil from rubber seeds are not used for applications with
high economic value. However, studies have shown that because of its
properties and abundance, rubber seeds poses a great potential in several
applications such as: (1) lubricant; (2) printing ink; (3) foaming agent in latex
foam; (4) alternative source for biodiesel production; (5) paints and coatings;
(6) nitrogenous fertilizers; and (7) a component for the formulation of
livestock feeds.
In this research, the proponents will utilize the extracted rubber seed
oil to produce formic acid, which add to the potential industrial applications of
rubber seeds. If this potential is to be realized, a series of processes has to be
undergone in order to obtain the product proposed.
B. PROCESS
B.1 Solvent Extraction
Being a conventional method, solvent extraction is the most widely
used technique, owing to its high efficiency in oil recovery (90 to 98%)
(Sharma et al., 2002). The advantages of solvent extraction over other
methods of oil extraction include higher oil recovery (about 95% of the oil
content could be obtained), larger processing capacity, and gives oil that
many considered to be of lower refining losses (Lager, 2006, Robbellen et
al.,1989 and Goss, 2004).
Thermal Oxidation of Glycerol from Rubber (Hevea
brasiliensis) Seed Oil for the Production of Formic Acid
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time,
stirring
speed
and
temperature
are
important
for
transesterification method.
Transesterification has two types according to the catalyst used: (1)
homogeneous transesterification; and (2) heterogeneous transesterification.
In most cases, homogeneous transesterification is employed because it was
the most economical process which requires only low temperature and
pressure (Refaat, 2010).
Base-catalyzed transesterification, which falls under homogeneous
transesterification, is the action of one alcohol group from a strong base
displacing another from an ester, referred to as alcoholysis. It consists of
three consecutive reversible reactions.
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C3 H 8 O3 + 4 H 2 O 2 3 HCOOH +5 H 2 O
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C. PRODUCT
Formic Acid
Formic acid is the simplest carboxylic acid. Its chemical formula is HCOOH
or HCO2H. It is an important intermediate in chemical
synthesis
comes from
isolation by
Formic acid is the first in the series of saturated monobasic carbon acids.
It is widely used in pharmaceutics, perfumery, paper and food production as
well as in agriculture, tanneries and textile production.
Table 1.6 Industrial Application of Formic Acids
Industry
Leather
Textile
Rubber
Home Care, Industrial
and Institutional
Cleaning
Chemical
Agriculture
Oil
Road Works
Pharmaceutical
Industrial Applications
Application
Tanning; Dye-fixing Agent
Neutralizing Agent; pH Adjuster
Coagulant
Descaler; Biocide
Hydride Donor; Carbon Dioxide Production;
Storage and Transportation Medium for
Hydrogen
Antibacterial Preservative; Pesticide
CaCO3 Dissolver; Well Drilling
Deicing Agent
Active Ingredient in OTC Drug Products
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Artificial Flavors
Artificial Perfumes
Fuel Cell
Formic Acid
Color
Odor
Boiling Point
Viscosity
Density
Flashpoint
pH
Colorless Liquid
Pungent
101 0C
1.8 cp
1.22 g/mL
56.11 0C
2.3
3400-2400
O-H stretch
1730-1650
C=O stretch
Year
2014
2013
2012
2011
2010
Importation (kg)
947,669
813,644
644,810
445,550
849,978
The table above shows the importation of formic acid from 2010-2014
which is graphically presented in Figure 1.9. The highest exportation was
recorded on 2014 amounting to 947,669 kg. Although the records are slightly
fluctuating in value there is still a great demand from this commodity.
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2010
2011
2012
2013
2014
11
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B. Solvent Extraction
Presented in Table 1.4 are studies on the effects of different extraction
methods used on rubber seed oil. It is shown that the oil yield varied
depending on the extraction method that was used.
Table 1.4 Extraction Method of Different Studies
Author
Bokhari et al.
Raw
Material
Rubber Seed
Extraction
Method
Solvent
Parameters
Oil Yield
Solvent Used: n-
33.56 %
12
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Study
(2010)
Kernel
Extraction
with Stirring
Soxhlet
Extraction
Ebewele et
al. (2010)
Rubber Seed
Kernel
Mechanical
Extraction
MohdSetapar et al.
(2014)
Rubber Seed
Kernel
Soxhlet
Extraction
Soxhlet
Extraction
Wildan et al.
(2012)
Solid Waste
Rubber Seed
Solvent
Extraction
with Stirring
Hexane
Extraction Time: 4
hours
Temperature: 60C
Time: 4 hours
Temperature:
Boiling Point of
Solvent.
Particle Size: 1.16
mm
MC: 10% (wt),
Temperature: 70C
Pressure: 8 MPa.
Solvent: Petroleum
Ether
Time: 6 hours
Ratio: 1:15 solid to
solvent ratio.
Solvent: n-Hexane
Amount of Solvent:
400 mL
Circulation: 30
Solvent: n-Hexane
Amount of Solvent:
400 mL
Time: 5 hours
Not Stated
45.03%
60%
19.80%
17.37%
In the study of Ebewele et al. (2010), oil from rubber seeds were
extracted using soxhlet extractor with n-hexane as solvent. The extraction
was carried for four hours at temperature corresponding to the boiling point
of solvent. The hexane-oil mixture was separated using a rotary evaporator.
The effect of particle size was also studied where the particle size used range
from 1.16-3.36 mm using standard methods ASTM E11. Prior to processing,
the rubber seeds were dried to a moisture content of 7% which is safe for
storage and then place in a warehouse.
Results showed that the highest oil yield (45.03%) was obtained at the
smallest particle size (1.16 mm) while the lowest oil yield was obtained at the
highest particle size of 3.36 mm. It does show that less oil is extracted from
Thermal Oxidation of Glycerol from Rubber (Hevea
brasiliensis) Seed Oil for the Production of Formic Acid
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B. Base-Catalyzed Transesterification
Base catalyzed transesterification will be employed in the study due to
the fact that rubber seed was reported to have high free fatty acid content of
17% (Pandey, 2008). Conventionally, it must undergo acid catalyzed
esterification before base catalyzed transesterification to reduce the FFA
content, which would yield greater amount of biodiesel (Ribeiro et al., 2011).
Since this study focuses more on yielding less ester and more glycerol, base
catalyzed transesterification will be employed in this study.
For transesterification, the usual base catalyst used are sodium
hydroxide, potassium hydroxide, and calcium hydroxide. These catalyst has
varying effects in the yield of biodiesel and glycerol. Biodiesel with the best
properties was obtained using potassium hydroxide as catalyst in many
studies (Refaat et al., 2008). In the case of the alcohol, most of the time,
Thermal Oxidation of Glycerol from Rubber (Hevea
brasiliensis) Seed Oil for the Production of Formic Acid
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C. Thermal Oxidation
Different ways of producing formic acid via oxidation of glycerol are
presented on the table below.
Table 1.4 Synthesis of Formic Acid from Glycerol
Author
Raw Material
Method
Used
Zhang et al.
(2013)
Crude Glycerol
from BaseCatalyzed
Transesterification
of Fats
Hydrothermal
Oxidation
reaction with
Glycerol
Crude Glycerol
Partial
Oxidation of
Glycerol at
Hydrothermal
Condition
Watanabe et
al. (2014)
Parameters
Time: 40 s
Temperature:
250C
Oxidant: H2O2
(240%)
Time: 10 min
Temperature:
200C
Glycerol to
Oxidant Ratio:
1:3.5
Formic
Acid
Yield
34.7%
45%
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Author
Extraction of
Rubber (Hevea
brasiliensis) Seed
Oil Using Soxhlet
Method
MohdSetapar et
al.
Effects of
Temperature,
Pressure,
Preheating Time
and Pressing Time
on Rubber Seed Oil
Extraction Using
Hydraulic Press
Santoso, et
al.
Year
2014
Data Obtained
Solvent
Extraction
Drying Rubber
Seed Kernel
2014
Drying Rubber
Seed Kernel
18
Data Used
Solvent:
Petroleum
Ether, nHexane
Temp: 105C
MC: 7%
Purpose of the
drying process
is to reduce
the moisture
content so
that the
kernels are
safe to be
placed in the
storage.
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Extraction and
Characterization of
Rubber Seed Oil
Oil Extraction
Process from Solid
Waste Rubber
Seed by
Soxhletation and
Extraction Solvent
by Stirring
Methods
Consideration of
the Extraction
Process and
Potential Technical
applications of
Nigerian rubber
seed oil
Optimization of the
Parameters that
Affects the Solvent
Extraction of
Crude Rubber
Seed Oil
Basetransesterification
Asuquo, et
al.
2012
Drying Rubber
Seed Kernel
Solvent
Extraction
Wildan et al.
2012
Solvent
Extraction with
Stirring
Ebewele et
al.
2010
Bokhari et al.
2010
Vasutheavan
2012
Drying Rubber
Seed Kernel
MC: 7-13%
Solvent
Extraction
Time: 4 hours
Temp: Boiling
Point of
Solvent
Solvent
Extraction
Basetransesterificatio
n
19
Seeds were
grounded
using mortar
and pestle
into a paste in
order to
weaken and
rupture the
cell.
Solvent: nHexane
Amount of
Solvent: 400
mL
Solvent: nHexane,
Diethyl Ether
Amount of
Solvent: 400
mL
Time: 1-7
hours
Solvent: nHexane
Ratio of Kernel
to Solvent: 1:4
Time: 2-4
hours
Temperature:
below 64oC
Ratio of Oil to
Ethanol: 1:6
Amount of
Catalyst:
0.5 %wt
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Zhang et al
Tohji et al.
2013
Thermal
Oxidation
2014
Thermal
Oxidation
20
Temp : 50oC
Oxidant agent
: Hydrogen
Peroxide
Temp: 150 450 C
Chemical
Reaction
Scheme
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