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“Thermal Oxidation of Glycerol from Rubber (Hevea brasiliensis) Seed Oil for the Production of Formic Acid”

Project Study

Pamantasan ng Lungsod ng Maynila College of Engineering and Technology

Chemical Engineering Department

REVIEW OF RELATED LITERATURE

A.RAW MATERIALRubber 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 a relatively stable high temperature, and at the same time, continuous moisture throughout the year.

Origin of Rubber TreeThe 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

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Figure 1.1 Rubber Seeds

Figure 1.2 Rubber Tree Plantation


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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 SizeNo. of Rubber

TreesBrgy. Ilayang,

Magdalena (Laguna)Atty. Ceriaco

Sumaya 5-hectare 3, 000Brgy. Layugan,

Pagsanjan (Laguna)Mr. Alex

Pactananan 2.5-hectare 2, 500

Quezon Mrs. Ernida Reynoso 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

2Figure 1.3 Bleeding

of rubber tree


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the tree that is utilized is the bark. Large biomass from the rubber tree are left unutilized, specifically the rubber seeds.

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 a 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.

Parts of Rubber Fruit

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

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Figure 1.4 Ripe rubber fruit

Kernel

Shell

Figure 1.6 Rubber Seed (Shell and

Figure 1.5 Rubber fruit, capsule, and seed

Rubber

Seed

Capsule


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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 Percent ContentOil 45.63Ash 2.71

Protein 22.17Carbohydrate 24.21

Others 5.28Source: 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 17-22% 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 AcidsCarbon Atoms :

Number of Double Bonds

Percent Composition

Palmitic Acid C16:0 10.29Stearic Acid C18:0 8.68Oleic Acid C18:1 20.07

Linoleic Acid C18:2 58.50Linolenic Acid C18:3 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 OilProperty Percentage

Specific gravity 0.9Viscosity at 40 °C (mm2/s) 66.2

Flash point (°C) 198.0Calorific value (MJ/kg) 37.5Acid value (mg KOH/g) 34.0

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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.PROCESSB.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).

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 64-69 ̊ºC, the maximum possible temperature to prevent the

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solvent from boiling is 60ºC. 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 TransesterificationTransesterification of vegetable or fruit seed oils is conventionally

carried out by subjecting the pre-extracted oil to treatment with the 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

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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 TransesterificationThe 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):

C3H 8O3+4H2O2→3HCOOH+5H 2O

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Figure 1-7. Reaction Mechanism for Thermal Oxidation

C.PRODUCTFormic Acid

Formic acid is the simplest carboxylic acid. Its chemical formula is H C O OH 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.

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

Industrial ApplicationsIndustry ApplicationLeather Tanning; Dye-fixing AgentTextile Neutralizing Agent; pH AdjusterRubber Coagulant

Home Care, Industrial and Institutional

CleaningDescaler; Biocide

Chemical Hydride Donor; Carbon Dioxide Production; Storage and Transportation Medium for

HydrogenAgriculture Antibacterial Preservative; Pesticide

Oil CaCO3 Dissolver; Well Drilling

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Fig. 2-8. Molecular formula of Formic Acid

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https://en.wikipedia.org/wiki/Formate

https://en.wikipedia.org/wiki/Ester

https://en.wikipedia.org/wiki/Distillation

https://en.wikipedia.org/wiki/Formica

https://en.wikipedia.org/wiki/Latin

https://en.wikipedia.org/wiki/Chemical_synthesis

https://en.wikipedia.org/wiki/Hydroxide

https://en.wikipedia.org/wiki/Oxygen

https://en.wikipedia.org/wiki/Carbon

https://en.wikipedia.org/wiki/Hydrogen

https://en.wikipedia.org/wiki/Chemical_formula

https://en.wikipedia.org/wiki/Carboxylic_acid


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Road Works Deicing AgentPharmaceutical Active Ingredient in OTC Drug Products

Food Artificial FlavorsFragrance Artificial Perfumes

Energy Fuel Cell

C.2 Properties of Formic AcidTable 1.7 Physical and Chemical Properties of Formic Acid

Formic Acid

Color Colorless LiquidOdor Pungent

Boiling Point 101 0CViscosity 1.8 cpDensity 1.22 g/mL

Flashpoint 56.11 0C

pH 2.3Source: Chemical Book; Engineering Toolbox (2010)

Table 1.8 FTIR Peak Values of Formic AcidFTIR peak value(Carboxylic Acid)

3400-2400 O-H stretch1730-1650 C=O stretch

Source: Principal IR Absorptions for Certain Functional Groups

Table 1.9 Importation of Formic Acid in the Philippines

Year Importation (kg)2014 947,6692013 813,6442012 644,8102011 445,5502010 849,978

Source: UN Comtrade Database (2015)

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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.

2010 2011 2012 2013 20140

100,000200,000300,000400,000500,000600,000700,000800,000900,000

1,000,000

Importation of Formic Acid in Philippines (2010 - 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 105°C. The process was done until

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constant weight was achieved. The rubber seed contain approximately 7% of moisture after 4 hours of drying using oven at 105°C. 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 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.

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Table 1.4 Extraction Method of Different Studies

Author Raw Material

Extraction Method Parameters Oil Yield

Bokhari et al. (2010)

Rubber Seed Kernel

Solvent Extraction

with Stirring

Solvent Used: n-Hexane

Extraction Time: 4 hours

Temperature: 60°C

33.56 %

Ebewele et al. (2010)

Rubber Seed Kernel

Soxhlet Extraction

Time: 4 hoursTemperature:

Boiling Point of Solvent.

Not Stated

Mechanical Extraction

Particle Size: 1.16 mm

MC: 10% (wt), Temperature:

70°C Pressure: 8 MPa.

45.03%

Mohd-Setapar et al. (2014)

Rubber Seed Kernel

Soxhlet Extraction

Solvent: Petroleum Ether

Time: 6 hoursRatio: 1:15 solid to

solvent ratio.

60%

Wildan et al. (2012)

Solid Waste Rubber Seed

Soxhlet Extraction

Solvent: n-HexaneAmount of

Solvent: 400 mLCirculation: 30

19.80%

Solvent Extraction

with Stirring

Solvent: n-HexaneAmount of

Solvent: 400 mLTime: 5 hours

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,

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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 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 60°C. 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.

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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 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 n-hexane 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).

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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, 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

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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 formation. Thus, the researchers decided to fix the methanol-to-oil ratio at 6:1.

C. Thermal OxidationDifferent 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 Parameters

Formic Acid Yield

Zhang et al. (2013)

Crude Glycerol from Base-Catalyzed

Transesterification of Fats

Hydrothermal Oxidation reaction with

Glycerol

Time: 40 sTemperature:

250°C Oxidant: H2O2

(240%)

34.7%

Watanabe et al. (2014) Crude Glycerol

Partial Oxidation of Glycerol at Hydrothermal Condition

Time: 10 minTemperature:

200°C Glycerol to

Oxidant Ratio: 1:3.5

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 150-450°C 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

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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), 250°C (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 glycerol was oxidized at a reaction temperature of 200°C 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 H2O2 as the oxidant in varying temperature (100-200°C), time (1-5minutes), and Glycerol to H2O2 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 Year Data Obtained Data Used

Extraction of Rubber (Hevea

brasiliensis) Seed Oil Using Soxhlet

Method

Mohd-Setapar et

al.201

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Solvent Extraction

Solvent: Petroleum Ether, n-Hexane

Drying Rubber Seed Kernel

Temp: 105°CMC: 7%

Effects of Temperature,

Santoso, et al.

2014

Drying Rubber Seed Kernel

Purpose of the drying

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Pressure, Preheating Time

and Pressing Time on Rubber Seed Oil Extraction

Using Hydraulic Press

process is to reduce the moisture

content so that the

kernels are safe to be

placed in the storage.

Extraction and Characterization

of Rubber Seed OilAsuquo, et

al.201

2Drying Rubber Seed Kernel

Seeds were grounded

using mortar and pestle

into a paste in order to

weaken and rupture the

cell.

Oil Extraction Process from Solid

Waste Rubber Seed by

Soxhletation and Extraction Solvent

by Stirring Methods

Wildan et al. 2012

Solvent Extraction

Solvent: n-Hexane

Amount of Solvent: 400

mL

Solvent Extraction with

Stirring

Solvent: n-Hexane,

Diethyl EtherAmount of

Solvent: 400 mL

Time: 1-7 hours

Consideration of the Extraction Process and

Potential Technical

applications of Nigerian rubber

seed oil

Ebewele et al.

2010

Drying Rubber Seed Kernel MC: 7-13%

Solvent Extraction

Time: 4 hoursTemp: Boiling

Point of Solvent

Optimization of the Parameters that Affects the

Bokhari et al.

2010

Solvent Extraction

Solvent: n-HexaneRatio of

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Solvent Extraction of

Crude Rubber Seed Oil

Kernel to Solvent: 1:4Time: 2-4

hoursTemperature: below 64oC

Base-transesterification Vasutheavan 201

2Base-

transesterification

Ratio of Oil to Ethanol: 1:6Amount of Catalyst: 0.5 %wt

Temp : 50oCFormation of

formic acid from glycerine using a

hydrothermal reaction

Zhang et al 2013

Thermal Oxidation

Oxidant agent : Hydrogen Peroxide

Temp: 150 - 450 C

Formic Acid Production by Hydrothermal Oxidation of

Biomass-Derived Carbohydrate

Tohji et al. 2014

Thermal Oxidation

Chemical Reaction Scheme

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