RRL Only (31jan2016)

Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology

Chemical Engineering Department
REVIEW OF RELATED LITERATURE

A. RAW MATERIAL
Rubber Seeds
Rubber
seeds
are
side
products
of
rubber trees. In the Philippines, the total land

area planted with rubber trees has been
reported to be 217,686 hectares according to
the 2014 data from Bureau of Agricultural
Statistic (http://countrystat.psa.gov.ph).
Scientifically
known
as
Hevea
brasiliensis, rubber tree is a fast growing tree

cultivated in geographical areas where soil has
Figure 1.1 Rubber Seeds
a relatively stable high temperature, and at the

same time, continuous moisture throughout the year.
Origin of Rubber Tree
The natural rubber tree (Hevea brasiliensis) is a native of South
America introduced to Southeast Asia including Thailand, Malaysia, China,
India, Indonesia, Sri Lanka, Cambodia, Vietnam, and the Philippines during
the 19th century. Rubber trees can grow to a height of 18 to 39 meters and
they grow best in warm and moist climate ranging from 70-95 Fahrenheit or
21-35 Centigrade with an annual rainfall of 80-120 inches (2,000-3,000 mm).
Availability of Rubber Seed
It has been reported that the number of
mature trees in 2011 was 42.06 million trees
located nationwide. The plantations are located
mostly in Mindanao, however rubber trees are
Figure 1.2 Rubber Tree

Plantation
Thermal Oxidation of Glycerol from Rubber (Hevea
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brasiliensis) Seed Oil for the Production of Formic Acid
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now grown in Aborlan, Palawan; Isogod, Quezon; Sta. Maria, Laguna; and Sta.
Cruz, Laguna (Calasagsag, 2011).
Propagation of Rubber Trees
First Laguna Rubber is a business enterprise duly registered with the
Bureau of Domestic Trade (DTI), as a single proprietor, primarily engage in
rubber propagation, planting and marketing of rubber cup lumps in local and
international market. The business started on January 2006. This single
proprietorship was changed to a corporation and now be called First Laguna
Agro-Forestry Development Corporation, with an office address at 71
Magnolia St., Remedios Country Homes III, Brgy. San Jose, Sta. Cruz, Laguna.
At present, First Laguna Rubber has penetrated most of the provinces in the
island of Luzon, namely: Laguna, Quezon, Batangas, Cavite, Bulacan, Nueva
Ecija, Nueva Viscaya, and Cagayan Valley, with an approximated total area of
seven hundred (700) hectares, fully planted of rubber trees.
Table 1.1 Some Rubber Plantations in Luzon
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
Source: National Agricultural and Fishery Council (2012)
Primarily, these plantations are intended for the production of high

quality latex. The collected latex serves as the primary product that can be
obtained from the crop. This latex is located mostly on the bark of the tree,
making it the most important of the crop. Basically, the only part of the tree
that is utilized is the bark. Large biomass from the rubber tree are left
unutilized, specifically the rubber seeds.
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Figure 1.3 Bleeding

of rubber tree

A data from the Food and Agriculture Organization
reported that a total of 161,565 hectares of rubber tree
plantation
in
the
Philippines
was
able
to
generate
approximately 250,941 seeds for the year 2011. Despite its

abundance, these seeds are often neglected.
Fruits and Seeds
Only
small
proportion
of
female
flowers set fruit and of these 30-50% fall after

a month and more fall off later. The mature
fruit is a large, compressed, 3-lobbed capsule,
3-5 cm in diameter, with 3 oil-containing
seeds. The capsule bursts open at the end of
the rainy season with a characteristic loud
bang, similar to a rifle shot. The seeds are
then collected for sowing in the nursery.
Figure 1.4 Ripe rubber
Parts of Rubber Fruit
fruit
Rubber fruit
Capsule
Seed
Figure 1.5 Rubber fruit, capsule, and seed

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Shell
Kernel

Figure 1.6 Rubber Seed (Shell and kernel)
Parts of Rubber Seed

A rubber seed usually matures during dry periods between August to
November. Its weight varies from 3 to 5 gram. It is comprised of 40% kernel,
35% shell and the remaining is a balanced moisture (Iyayi et al., 2008). From
these seeds, there are two obtainable products namely the oil and the cake.
The tabular presentation shown below indicates the complete chemical
composition of rubber seeds.
Table 1.3 Chemical Composition of Rubber Seeds
Composition
Oil
Ash
Protein
Carbohydrate
Others
Percent Content
45.63
2.71
22.17
24.21
5.28
Source: In Situ Transesterification of Rubber Seed (Hevea brasiliensis) by Abdulkadir et al.

(2014)
The oil that can be extracted from these oil-bearing seeds is

characterized to be semi-drying, yellowish in coloration, and consists of 1722% saturated fatty acid and 17-82% unsaturated fatty acid (Iyayi et al.,
2008). The complete fatty acid composition of rubber seed oil is presented on
Table 1.3.
Table 1.4 Fatty Acid Composition of Rubber Seed Oil
Fatty Acids
Palmitic Acid
Carbon Atoms :
Number of Double
Bonds
C16:0

Percent Composition
10.29
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Stearic Acid
Oleic Acid
Linoleic Acid
Linolenic Acid
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)
Table 1.5 Fatty Acid Composition of Rubber Seed Oil
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).
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The method used to extract rubber (Hevea Brasiliensis) seed oil is

solvent extraction. The oil of rubber seed is non-polar, therefore, it is easier to
be extracted using non-polar solvent. Among the existing non-polar solvents
used for oil extraction, hexane is yielding up to 98% of the oil contained
within the plant cell, and leaving half percent of the total residual oil present
in oil-bearing materials (Wildan, 2012). Considering that the boiling point of
hexane, the most efficient solvent for oil extraction, ranges typically from 6469C, the maximum possible temperature to prevent the solvent from boiling
is 60C. High solubility of oils and fats in it are the properties that make it
suitable for use in extraction of oil from oil-bearing materials. Hexane is
highly stable and largely unreactive (Ahmad, 2000).
The maximum extraction occurs at a speed of 200 rpm for most
solvents including hexane. Increasing the speed of mixing gives greater
chances for the molecules to come in contact with one another. However,
after reaching the maximum speed, the oil extracted becomes constant
because most of the fatty acids have already been extracted during the
maximum speed; thus, it will no longer result any further extraction of oil
(Thermo Scientific, 2008). The best extraction time is 2-4.5 hours and the
yield increased with increasing solid to solvent ratio up to 1:4. (Bokhari et. al,
2010).
B.2 Base-catalyzed Transesterification
Figure ___ Reaction Scheme of Transesterification
Transesterification of vegetable or fruit seed oils is conventionally

carried out by subjecting the pre-extracted oil to treatment with the
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appropriate alcohol, in the presence of an acid or an alkaline catalyst.
Selecting a suitable alcohol, catalyst, amount of catalyst, oil to solvent ratio,
reaction
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.
The first step is the conversion of
triglycerides to diglycerides, followed by the conversion of diglycerides to

monoglycerides, and finally monoglycerides into glycerol, yielding fatty acid
ester molecule from each glyceride at each step.
Figure ____ Three Steps Involved in Base-Catalyzed Transesterification
The catalyst and solvent react together to form a nucleophile which is

responsible for abstracting hydrocarbon groups from a triglyceride to form
fatty acid esters and glycerol. The complete reaction mechanism is below.

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Figure ___ Reaction Mechanism for Base-Catalyzed Transesterification

(B is a base and R1 to R4 are hydrocarbon groups)
B.3 Thermal Oxidation

Thermal oxidation degrades the carbohydrates, in this case glycerol,
into formic acid. In thermal oxidation, the C-C bond of glycerol is cleaved
using the oxidant agent, hydrogen peroxide, to form the carboxylic acid
(formic acid). Hydrogen Peroxide was chosen as the oxidant because
compared to other oxidants, chlorine dioxide and potassium permanganate,
H2O2 has the distinct advantage of producing only water as a by-product
(Hydrogen Peroxide Chemical Properties) thus making the reaction simpler
and easier to handle. 1 mol of glycerol could produce 3 mol of formic acid as
shown in the equation below (Tohji, et al. 2014):
C3 H 8 O3 + 4 H 2 O 2 3 HCOOH +5 H 2 O

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Figure 1-7. Reaction Mechanism for Thermal Oxidation
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
and occurs naturally, most notably in some ants. Its name
comes from
the Latin word for ant, formica, referring to its early
isolation by
the distillation of ant bodies. Esters, salts, and the

anions derived from formic acid are referred to as
formates.
Fig. 2-8. Molecular

formula of Formic Acid
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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Food
Fragrance
Energy
Artificial Flavors
Artificial Perfumes
Fuel Cell
C.2 Properties of Formic Acid

Table 1.7 Physical and Chemical Properties of Formic Acid
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
Source: Chemical Book; Engineering Toolbox (2010)
Table 1.8 FTIR Peak Values of Formic Acid
FTIR peak value

(Carboxylic Acid)
3400-2400
O-H stretch
1730-1650
C=O stretch
Source: Principal IR Absorptions for Certain Functional Groups

Table 1.9 Importation of Formic Acid in the Philippines
Year
2014
2013
2012
2011
2010
Importation (kg)
947,669
813,644
644,810
445,550
849,978
Source: UN Comtrade Database (2015)
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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Importation of Formic Acid in Philippines (2010 - 2014)
2010
2011
2012
2013
2014
Figure 2-9 : Importation of Formic Acid in Philippines (2010 - 2014)
REVIEW OF RELATED STUDIES

A. Drying of Rubber Seed
In the study of Mohd-Setapar et al. (2014), 10 grams of 0.5 mm of
rubber seeds were heated in an oven at 105C. The process was done until
constant weight was achieved. The rubber seed contain approximately 7% of
moisture after 4 hours of drying using oven at 105C. It has been previously
reported by other studies that the optimum range of moisture content in
oilseed processing is between 5 to 13%. On the otherhand, in the study of
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Asuquo et al. (2012), the seeds were dehulled, cleaned and dried under the
sun for a day and later dried in the oven for three hours at 50 C to ensure
that water and moisture were removed. The seeds were immediately
grounded using mortar and pestle into a paste in order to weaken and
rupture the cell.
According to Ebewele et al. (2010), the optimum moisture content of
rubber seed oil extraction is 10%. They also reported that higher oil yield was
observed at a lower moisture content of 7% up to 10 to 13% with exceptional
to very low or higher temperature. This is because, during the extraction
process, the moisture in the seeds acts as a heat transfer medium and helps
in coagulation of protein for oil yield. Therefore, too high or too low
temperature may disturb the function of the moisture in oilseed processing.
Santoso et al. (2014) studied the effects of temperature, pressure,
preheating time and pressing time on rubber seed oil extraction using
hydraulic pressing. The rubber seed kernels are then dried for 12 hours at
70oC. The purpose of the drying process is to reduce the moisture content in
the rubber seed kernels so that the kernels are safe to be placed in the
storage. The dried kernels are then flaked until the flakes are about 0.5-0.8
mm in size (mesh no.-20+30). The smaller the seed particle size, the higher
the oil yield can be obtained.
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 %

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(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
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the larger particles to the smaller sized particles. It was also stated in the
study that this phenomenon could be contributed to the fact that smaller
particles have larger amount of surface area as well as an increased number
of ruptured cells resulting in a high oil concentration at the particle surface.
In the study of Bokhari et al. (2010), oil from rubber seeds were
extracted using solvent extractor with n-hexane as solvent. The extraction
was carried for 4 hours at temperature corresponding to less than the boiling
point of solvent, this case is 60C. The hexane-oil mixture was separated
using a rotary evaporator. 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. The oil yield from this process is 33.56%.
A recent study conducted by Mohd-Setapar et al. (2014), made used of
soxhlet extraction which refers to the preferential dissolution of oil by
contacting oilseeds with a liquid solvent to extract rubber seed oil. In this
study, three variables were studied which was the choice of solvent
(petroleum ether, n-hexane, ethanol or water), extraction time and solid to
solvent ratio. It was found that the oils from n-hexane and petroleum ether
extractions were both golden yellowish, with the original odor of rubber
(Hevea Brasiliensis) seed. This is because both solvents have low polarity
which only extract the glyceride compound in the seeds and are very miscible
in the oil. On the other hand, white particles were observed to be extracted
together with the oil when using a polar solvents of water and ethanol:water.
Therefore, rubber seed oil is non-polar lipid. Lastly, the maximum yield (60%)
was obtained under the following conditions: petroleum ether as solvent, 6
hours, and 1:15 solid to solvent ratio.
Besides that, they also reported that easy solvent recovery from the
meal is also an important trait of an ideal solvent. The ideal solvent should be
non-flammable or has a narrower range of explosive limits to avoid or reduce
the possibility of fire or explosion during extraction. The extraction solvent
also should be non-reactive to the meal or oil, as well as the extraction
equipment. On the other hand, ideal solvents should also have high purity to
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exhibit more uniform operating characteristics, as well as having low
solubility in water for easier separation. Ultimately, an ideal solvent should be
easily available at low prices.
Moreover, the study of Wildan et al. (2012) compared two extraction
methods of rubber seed oil namely soxhelation and solvent extraction by
stirring. The solvent used in each of extraction methods are n-hexane, diethyl
ether and ethanol.
For soxhlet extraction method, first weighed 40 gram waste rubber
seed added with 400 ml of solvent was used varying the amount of
circulating extraction soxhlet to 10, 20, 30, 40, and 50 circulation. For the
method of extraction with stirring, 40 grams of rubber seed pulp was put into
a glass beaker with 400 ml solvent, stirring by magnetic stirrer with
extraction time variety of 1, 2, 3, 4, 5, 6, and 7 hours. Based on the results,
the optimum circulation amount was 30 times circulation with the use of nhexane as solvent generating a yield of 19.80 %. On the contrary, the method
of extraction with stirring was found to have an optimum operating time of 5
hours with the use of n-Hexane as solvent. The oil yield was 17.37% by
weight.
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,
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methanol is used as solvent for transesterification. Ethanol is less stable than
methanol, being a hydrophilic this interferes in the reaction which results to
lesser yield of product. Among these solvents, methanol works best because
it has the least molecular weight. The molecular weight of methanol is 32.05
g/gmole while the molecular weight of ethanol and propanol are 46.08 and
60.11 g/gmole respectively. Increasing the chain length of RO-(alcohol) group
results in the increase of reaction rate and causes steric hindrance which
prolonged the reaction.
Glycerol is produced by using vegetable oils and animal fats. The main
components of vegetable oils and animal fats are triglycerides or also known
as esters of fatty acids attached to a glycerol. The triglycerides contain
several different fatty acids. These fatty acids differ from each other by their
physical and chemical composition. Hence, these fatty acids will be the
parameter in influencing the property of the vegetable oil and animal fat. This
oil contains high viscosity and that is the main obstacle to use it as a fuel.
Chemical reactions are used to lower the viscosity of these oils. In the
reaction, triglycerides are converted into fatty acid methyl ester (FAME), in
the presence of short chain alcohol, such as methanol or ethanol, and a
catalyst, with glycerol as a by-product. The optimum parameters for this step
is as follows: 1:6 molar ratio of oil to ethanol, 0.5 wt. % of base catalyst
(NaOH) and temperature of 50oC. (Vasutheavan, 2012).
The stoichiometry of the transesterification requires three moles of
alcohol per mole of vegetable oil to yield three moles of fatty ester and one
mole of glycerol Pryde (1982). When excess methanol is used (15:1 molar
ratio), natural separation of the ester and glycerol layers after the reaction is
possible. However, at the theoretical ratio of 3:1, the two layers were not
observed but the reaction mixture remained semi-solid throughout the
reaction and after 6 hours, it apparently reached the equilibrium with
significant amount of mono-, di- and triacylglycerols remaining. In the 6:1
molar ratio of reactants, natural separation of ester and glycerol was
observed with a solid glycerol layer and a semi-solid reaction mixture during
the reaction which indicates the formation of two layers. A further increase in
the molar ratio beyond 6:1 has no significant increase in the rate of product
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formation. Thus, the researchers decided to fix the methanol-to-oil ratio at
6:1.
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%
Zhang et al. (2013) proposed a process for producing formic acid by

hydrothermal oxidation reaction with glycerol, wherein glycerol and oxidant
are subjected to a hydrothermal oxidation reaction, H2O2 as oxidant, at a
temperature range of 150-450C and under pressure equal to or more than
the saturated vapor pressure at the temperature. Glycerol produced from
fats, typically from the base-catalyzed transesterification of fats to obtain
fatty ester, are preferably used as the raw material. The effect of different
parameters in the reaction were also studied. The study concludes that the
optimal parameters for the hydrothermal oxidation are the following: 240%
H2O2 supply (oxidant), 250C (temperature), 40 seconds (time), and 1.2 M
NaOH (catalyst) corresponding to a yield of 34.7% formic acid.
A recent study done by Watanabe et al. (2014) involves the partial
oxidation of glycerol into formic acid at hydrothermal condition wherein
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glycerol was oxidized at a reaction temperature of 200C and a reaction time
of 1 min. 1 mole of glycerol was partially oxidized with 3.5 moles of hydrogen
peroxide in order to produce formic acid.
In order to find the optimum parameters for the maximum yield of
formic acid, the researchers decided to conduct an experiment wherein crude
glycerol, obtained from the base catalyzed transesterification of oil from plant
fat (rubber seed oil), is oxidized using H 2O2 as the oxidant in varying
temperature (100-200C), time (1-5minutes), and Glycerol to H 2O2 molar ratio
of 1:4. The stated parameters were based from the studies done by Zhang et
al. (2013) and Watanabe et al. (2014).
SUMMARY OF RELATED STUDIES

Title
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

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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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Formation of
formic acid from
glycerine using a
hydrothermal
reaction
Formic Acid
Production by
Hydrothermal
Oxidation of
Biomass-Derived
Carbohydrate
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
Project
Study

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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

REVIEW OF RELATED LITERATURE

rubber trees. In the Philippines, the total land

brasiliensis, rubber tree is a fast growing tree

Figure 1.1 Rubber Seeds

a relatively stable high temperature, and at the

Figure 1.2 Rubber Tree

Pamantasan ng Lungsod ng Maynila

Source: National Agricultural and Fishery Council (2012)

Primarily, these plantations are intended for the production of high

Figure 1.3 Bleeding

Pamantasan ng Lungsod ng Maynila

approximately 250,941 seeds for the year 2011. Despite its

flowers set fruit and of these 30-50% fall after

Parts of Rubber Fruit

Figure 1.5 Rubber fruit, capsule, and seed

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

Figure 1.6 Rubber Seed (Shell and kernel)

Parts of Rubber Seed

Source: In Situ Transesterification of Rubber Seed (Hevea brasiliensis) by Abdulkadir et al.

The oil that can be extracted from these oil-bearing seeds is

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

Table 1.5 Fatty Acid Composition of Rubber Seed Oil

Pamantasan ng Lungsod ng Maynila

The method used to extract rubber (Hevea Brasiliensis) seed oil is

B.2 Base-catalyzed Transesterification

Figure ___ Reaction Scheme of Transesterification

Transesterification of vegetable or fruit seed oils is conventionally

Pamantasan ng Lungsod ng Maynila

The first step is the conversion of

triglycerides to diglycerides, followed by the conversion of diglycerides to

Figure ____ Three Steps Involved in Base-Catalyzed Transesterification

The catalyst and solvent react together to form a nucleophile which is

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

Figure ___ Reaction Mechanism for Base-Catalyzed Transesterification

B.3 Thermal Oxidation

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

Figure 1-7. Reaction Mechanism for Thermal Oxidation

and occurs naturally, most notably in some ants. Its name

the Latin word for ant, formica, referring to its early

the distillation of ant bodies. Esters, salts, and the

Fig. 2-8. Molecular

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

C.2 Properties of Formic Acid

Source: Chemical Book; Engineering Toolbox (2010)

Table 1.8 FTIR Peak Values of Formic Acid

FTIR peak value

Source: Principal IR Absorptions for Certain Functional Groups

Source: UN Comtrade Database (2015)

Thermal Oxidation of Glycerol from Rubber (Hevea

Pamantasan ng Lungsod ng Maynila

Importation of Formic Acid in Philippines (2010 - 2014)

Figure 2-9 : Importation of Formic Acid in Philippines (2010 - 2014)

REVIEW OF RELATED STUDIES

Pamantasan ng Lungsod ng Maynila

Thermal Oxidation of Glycerol from Rubber (Hevea