EXPERIMENTAL
STUDY
PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology
Department of Chemical Engineering
METHODS OF RESEARCH
Data gathering is an essential step for ensuring the feasibility of the study. Here, the
researchers have gathered the data and information regarding the profile, properties and
availability of the raw material, the operating conditions that will yield high results, the market
viability and the standards properties of the desired product as well as the available testing
facilities were collected. The descriptive and experimental method were used to obtain all
necessary data and information needed in this study.
A. Descriptive Method
Descriptive research was conducted to gather information about the profile,
properties, availability and current status for both the copra meal (raw material) and alkyd
resin (product). The researchers gathered all the necessary information through electronic
sources, government websites and government agencies.
The historical data of the demand and supply of alkyd resin were gathered from
Philippine Statistics Authority. The information gathered were used specifically in the market
study to determine the market feasibility of the product. Also, the yearly production of coconut
in the Philippines as well as the properties and characteristics of copra meal were gathered
from Philippine Coconut Authority (PhilCoA). The information gathered were used as a basis
on the determination of the current amount of copra meal produced in the country and as a
basis on the typical composition of the raw material. Moreover, the researchers tried to gather
data on the standard properties of alkyd resin however, only Alkyd-based Metal Primer (for
Paint and Varnishes) Specifications were obtained. Lastly, the researchers made use of the
internet to access and collect several electronic books, journals, and theses that served as
the references and foundation of the study.
B. Experimental Method
The experimental method is the scientific undertaking of the research. The researchers
conducted the experimental study in the laboratory by considering different parameters
obtained on literature and studies to come up with the best quality of the product. The
produced alkyd resin was then tested through various testing facilities.
All of the experimentations involved in the study, which includes the preparation and
analysis of copra meal, pre-treatment and conditioning of copra meal, mannitol production
and alkyd resin production, were carried out in PLDTSFH-CHE Laboratory at Pamantasan ng
Lungsod ng Maynila (PLM).
The raw material and product were characterized in different testing facilities. First,
the proximate analysis of the raw material was conducted at the laboratory of Department of
Agriculture to determine moisture, crude oil, crude fiber, ash, and carbohydrate content of
copra meal. Next, the testing for the Fourier Transform Infrared Spectroscopy (FTIR) of
mannose, mannitol and the alkyd resin were carried out at De La Salle University Chemistry
Instrument and Research Testing Center and Adamson University Chemistry Laboratory. FTIR
analysis was performed to check the presence of chemical bonds and functional groups in
the samples. Finally, testing for the High-Performance Liquid Chromatography (HPLC) of alkyd
resin were carried out at University of Sto. Tomas - Analytical Services Laboratory. HPLC is a
technique used to separate, identify, and quantify each component in a mixture.
Esterification of Hydrolyzed Copra (Cocos nucifera) Meal for the Production of Alkyd Resin
Dionisio, C.P., Fulugan, C.L., Redublo, A.P.
PROJECT STUDY 45
PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology
Department of Chemical Engineering
The conceptual framework is the research paradigm which shows the overview of the
research study, and includes the methods applied to achieve the research objectives. In order
to determine the feasibility of the research project, three sections of the study were evaluated:
(1) Market Study, (2) Experimental Study, and (3) Technical Study.
First, data gathering was conducted wherein the researchers visited several
government institutions, and utilized various researches, books, and websites. The raw
material profile (status, generation, sources, and properties of copra meal), the alkyd resin
profile and its market demand and supply, the existing and conventional processes of alkyd
resin production, as well as the mechanism of reactions were collected. Moreover, various
journals provided insights that served as the foundation and basis of the literature and
experimentation in the study.
Next, the market study was conducted to analyze and determine the marketability of
the product, alkyd resin. Historical data of market demand and supply were gathered and
projected to evaluate its potential to be sold in the local market, and to determine the market
share and plant rated capacity. Marketing program were developed to meet the company’s
objectives, mission, and goals within the specific timeframe. Moreover, marketing strategies
were developed to let the product penetrate the local market and compete with the existing
products. As the marketability of the alkyd resin was proven, the experimentation was
conducted after.
Then, the experimental study was done in a laboratory scale. The copra meal was
analyzed to determine its moisture, oil, and carbohydrate content. Several process
parameters were varied to optimize the quality and quantity of the product produced. The
alkyd resin product was characterized using FTIR, HPLC, and its physical and chemical
properties were determined, which were compared to the standard and existing product
properties. The optimum parameter values from the experiment were used in the scaled-up
designs in the technical study.
Lastly, in the technical study, the detailed manufacturing process (DMP) was
presented to give an overview on how the manufacturing plant will operate. The input and
output of materials in each process were calculated through material and energy balances.
Moreover, suitable equipment for each process were chosen and designed together with the
piping systems, instrumentation and process control, and the wastewater treatment facility of
the manufacturing plant. Safety was also discussed as part of plant operations.
The completion of the market study, experimental study, and technical study
established the feasibility of the study.
The framework shown above presents the major parts in the experimental study: (1)
pretreatment of copra meal, (2) mannitol production, and (3) alkyd resin production, its sub-
process as well as the variation of parameters used in the study.
The pretreatment of copra meal consists of drying, grinding, and leaching. Drying was
performed on copra meal to reduce its moisture content by varying drying conditions such as
time and temperature. Then, it was grinded to reduce its particle size wherein the grinding
time was determined. Lastly, leaching was done to remove residual oil in the copra meal by
varying leaching conditions such as solvent type, ratio of copra meal to solvent, temperature,
and time. The oil content of the defatted copra meal after leaching was determined using
Soxhlet Apparatus to calculate the amount of oil removed.
The second part of the experimentation is the mannitol production which includes
hydrolysis, neutralization, and reduction. In hydrolysis, mannan was reacted with an acid to
produce the hydrolysate. Parameters such as acid type, acid concentration, ratio of defatted
copra meal to acid, temperature, and time were varied. Then, hydrolysate was neutralized to
remove protein from copra meal and increase its pH by varying the type and amount of
neutralizing agent used. It was then filtered to remove crude fiber, isolating the mannose in
liquid form. The total reducing sugar content of mannose was determined using Benedict’s
Solution test. Afterwards, mannose was reacted with sodium borohydride to produce
mannitol, and parameters such as ratio of sodium borohydride to mannose, temperature, and
time were varied. To determine if mannitol was produced, the melting point and hydroxyl value
was tested, and FTIR and HPLC analysis was performed.
The last part of the experimentation is the alkyd resin production which consists of
esterification. Mannitol was reacted with phthalic anhydride and benzoic acid to produce a
polyester, alkyd resin. The ratio of the three reactants, process temperature, and time were
varied in the study to determine the optimum conditions for this process.
EXPERIMENTAL METHOD
The experimental method was developed to produce alkyd resin from copra meal. In order
to achieve the desired product quality and to determine the most suitable operating
conditions for each process, several parameter variations obtained from different literature
and studies were considered.
Before the experiment proper, the carbohydrate, moisture, and oil content of copra meal
were determined by proximate analysis. The experimental method is divided into three parts.
First part is the pretreatment of the copra meal which consists of drying, grinding, and
leaching. The amount of moisture content after drying was determined by oven drying method
while amount of oil removed was determined through Soxhlet Method. Next part is the
mannitol production which comprises of hydrolysis, neutralization, reduction, and
evaporation. The hydroxyl value of mannitol was tested, as well as the FTIR analysis were
performed. Last part is the alkyd resin production is eesterification. Optimum parameter in
each process was determined by the highest percentage yield accompanied by qualitative
determination.
Qualitative analysis of alkyd resin such as Fourier Transform Infrared Spectroscopy (FTIR)
and High Performance Liquid Chromatography (HPLC) and quantitative analysis such as
viscosity, specific gravity, acid value, non-volatile content, and hydroxyl value were determined
to ensure the validity of the optimum parameters obtained in the experiment.
A dry-run of the whole experiment using the optimum parameters was done to determine
if there were any significant changes in the final product. The results from the laboratory-scale
experimentation was used in alkyd resin production in industrial scale.
A. General Objectives
To produce alkyd resin from copra meal that conforms to the properties of the standard
and commercial products shown in Table 3.2.
B. Specific Objectives
To determine the optimal operating conditions for each processes that would produce
alkyd resin with properties conforming to the standard and commercial product;
To calculate the percent yield of each processes that will be used as basis in upscaling
to industrial set-up;
To determine if the desired products from hydrolysis, reduction, and esterification were
produced by evaluating the peaks in the FTIR spectroscopy;
To identify the equivalent unit operation and equipment of each laboratory process and
apparatus.
EXPERIMENTAL STUDY
The experimental method of the study focused on performing the process in a laboratory
scale set-up. The experiment is divided into the following sections:
I. Raw Material
I-1. Copra Meal Collection
I-2. Characterization of Copra Meal
A. Proximate Analysis (Carbohydrate Content)
B. Equilibrium Moisture Content
II. Pretreatment of Copra Meal
II- 1. Drying
II-2. Grinding
II-3. Leaching
III. Mannitol Production
III-1. Hydrolysis
III-2. Neutralization
III-3. Reduction
III-4. Evaporation
IV. Alkyd Resin Production
IV-1. Esterification
V. Characterization of Alkyd Resin
1. Physical and Chemical Properties
2. FTIR of Alkyd Resin
3. HPLC
Reagents
The reagents used in the experimentation are summarized in Table 3.3 shown below.
The reagents were obtained from Chemistry and Chemical Engineering Laboratory, PLM and
purchased from Alyson’s Chemicals Enterprises Inc, located at 1425 Gregorio Araneta
Avenue, Quezon City and RB Chemodities in Bambang, Manila.
Solvents
Acetone
Petroleum ether Dissolves residual oil from copra
Leaching
Isopropanol meal
Hexane
Chloroform
Acids
Phosphoric Catalyzes the hydrolysis of beta-
Hydrolysis
Hydrochloric glycosidic bonds in copra meal
Sulfuric
Bases
Calcium Hydroxide Neutralizes any remaining acid in
Neutralization
Sodium Carbonate the hydrolysis step
Potassium Hydroxide
Quantitative Analysis of Used to quantify the amount of
Benedict’s Reagent
Mannose reducing sugars in the hydrolysate
Used to reduce mannose to
Sodium Borohydride Reduction
mannitol
Reacts with mannitol to form
Phthalic Anhydride
polyester, alkyd resin
Monobasic Acid Esterification
Benzoic Acid Acts as a modifier in alkyd resin
Oleic Acid production
Stearic Acid
Laboratory Laboratory
Description Description
Apparatus Apparatus
1000mL,
3-neck round A laboratory
bottom flask glassware used as Oven
the reacting vessel
in hydrolysis,
reduction, and Used for drying the
polymerization steps copra meal
1000mL in volume
with 3 ports for
material, and
equipment input
Beaker Blender
Hot Plate
Erlenmeyer Flask
Electrically-powered
Used to measure,
device used for
mix, and store liquid
heating with
and suitable for
magnetic stirrer.
heating liquids
Vials Syringe
Used to transfer
Used to store liquids small volume of
and reagents liquids from one
container to another
EXPERIMENTAL PROCEDURE
I. RAW MATERIAL
I-1. Copra Meal Collection
The copra meal to be used in the experimentation was obtained from Brgy. Calamias,
Ibaan, Batangas through Mr. Raul C. Alcazar.
From Table 3.5, 39.6% of carbohydrates is the desired component from copra meal. It
was pretreated to remove excess moisture and residual oil through drying and leaching,
respectively. Afterwards, it was hydrolyzed to remove crude fiber which was the unreacted
component during the reaction. Moreover, it was subjected to neutralization to precipitate out
the protein.
Prior to the experimentation, the equilibrium moisture content of copra meal was
determined. It is the moisture level where the particle neither gains nor loses moisture since
it is at equilibrium with the relative humidity of the surrounding environment. As shown in the
equation below, it is defined as the difference between the total moisture content and free
moisture content.
𝑿∗ = 𝑿𝑻 − 𝑿
Where: 𝑋 = Free Moisture Content
𝑋𝑇 = Total Moisture Content
𝑋 ∗ = Equilibrium Moisture Content
B-3. Objective
To determine the equilibrium moisture content of copra meal which will be used as a
basis for obtaining the optimum drying parameters for the pretreatment of the raw materials.
B-4. Hypothesis
The equilibrium moisture content of copra meal will be in the range of 4-5%
B-5. Procedure
1. Prepare 50 grams of copra meal and dry at 70C.
2. Weigh and record the mass of the dried copra meal every 30 minutes.
3. Stop the drying process when the difference in the mass of dried copra meal is
negligible.
B-8. Analysis
The obtained free moisture content of copra meal from the three trials are 8.2321%,
8.0036% and 8.1996% with an average value of 8.1451%. These low values of moisture
content indicates that the raw material is safe for long-term storage. However, according to
Geankoplis (1993), the moisture content of the material must be reduced to avoid microbial
growth.
The calculated value for the equilibrium moisture content based on the free moisture
content and the total moisture content is 4.1549% which falls between the typical ranges of
4-5% for copra meal.
B-9. Conclusion
The equilibrium moisture content of copra meal is 4.1549 %
The effectiveness of drying processes can have a large impact on product quality and
process efficiency in subsequent processes (Parikh, 2014). Raghavan, V. & Dev, S. (2012)
also stated that drying is important because of ease of handling due to reduction in bulk and
reduction in handling costs, and dry biomaterials are less prone to microbiological
degradation in storage. Thus, copra meal with an initial moisture content of 12.3% or 30.75
grams moisture content in 250 grams of copra meal was dried.
Optimum parameters such as drying temperature and time were determined based on
the equilibrium moisture content, wherein it is desirable to have a final moisture content close
to the equilibrium content.
30.75𝑔 − 10𝑔
𝐹𝑖𝑛𝑎𝑙 𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝐶𝑜𝑛𝑡𝑒𝑛𝑡 (%) = 𝑥100% = 8.30%
250𝑔
A-6. Analysis
After drying at different temperatures from 50C to 90C, it was observed that there is
no noticeable change in appearance of copra meal. The selection of the optimum drying
temperature is based on the final moisture content of the copra meal. The table shows that
there is a decrease in the final moisture content as the drying temperature increases giving
drying temperatures of 80C and 90C with the lowest amount of final moisture content.
However, among those two drying temperatures, the difference on the final moisture content
is very low at 0.40%, showing a minimal increment. Thus, the selected optimum drying
temperature is at 80C.
A-7. Conclusion
The optimum drying temperature is at 80C with a final moisture content of 8.30%
B-3. Procedure
1. Weigh 5 sets of 250 grams copra meal and dry each trial at 80C for 1hr, 2hrs, 3hrs,
4hrs and 5hrs respectively.
2. Weigh and record the mass of dried copra meal after drying.
Trial 1 2 3 4 5
Mass of CM (g) 250 250 250 250 250
Initial Moisture Content (g) 30.75 30.75 30.75 30.75 30.75
Initial Moisture Content (%) 12.3 12.3 12.3 12.3 12.3
Time (hour) 1 2 3 4 5
Mass of Dried CM (g) 240 236 233 230 230
Mass of Water Removed (g) 10 14 17 20 20
Final Moisture Content (g) 20.75 16.75 13.75 10.75 10.75
Final Moisture Content (%) 8.30 6.70 5.50 4.30 4.30
30.75𝑔 − 20𝑔
𝐹𝑖𝑛𝑎𝑙 𝐹𝑟𝑒𝑒 𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝐶𝑜𝑛𝑡𝑒𝑛𝑡 (%) = 𝑥100% = 4.30%
250𝑔
B-6. Analysis
It was observed that there is no noticeable change in appearance of copra meal after
drying at different drying time at a temperature of 80C. The selection of the optimum drying
time is based on the final moisture content of the copra meal. The table shows that there is a
decrease in the moisture content as the drying time increases resulting into lowest amount of
final moisture content at drying time of 4 hours and 5 hours. However, among those two, 4
hours was selected as the optimum drying time since constant weight was already achieved
after 4 hours of drying.
B-7. Conclusion
The optimum drying time for copra meal is 4 hours having a final moisture content of
4.30%
Size reduction is a process of reducing large solid unit masses to small unit masses,
coarse particles or fine particles, which leads to increase of surface area for reaction (Archana,
K., et.al., 2013) The dried copra meal was ground in order to rupture the cell and expose more
surface area necessary for the next processes. In addition to that, it also makes handling
easier in the subsequent processing steps.
Parameters such as mesh size and grinding time were varied. Optimum mesh size was
determined based on the highest oil removed when leached, while optimum grinding time was
chosen based on the percent recovery after grinding.
A-1. Objective
To determine the average particle size of copra meal which will be used as a basis for
selecting the optimum mesh size of ground copra meal.
A-2. Hypothesis
The average particle size of the copra meal would be 0.710 mm.
A-3. Procedure
1. Weigh 50 grams of dried copra meal using analytical balance; then place it in the
blender and grind it for 10 minutes.
2. Sieve the ground copra meal using Tyler sieve then weigh the mass retained in each
sieve screen.
3. Calculate the mass fraction in each sieve size and determine the average particle size.
Computing for the average particle size using the sieve screen sizes,
A-6. Analysis
The average particle size of the copra meal depends on the size range on which the
highest mass fraction was retained. From the experiment, it was observed that the highest
mass fraction passed through 0.710 mm-sieve but retained on 0.500mm-sieve, which
represents 35.63% of the dried copra meal introduced in the sieve tray. From this size range,
the average particle size of 0.605mm was computed.
A-7. Conclusion
The average particle size of the dried copra meal is 0.605 mm.
B-1. Objective
To determine the optimum mesh size of dried copra meal that would yield high oil
removal when leached.
B-2. Hypothesis
Smaller particle size would result to high oil removal, thus mesh 60 (0.250mm) would
be the optimum mesh size.
B-3. Procedure
1. Weigh 5 sets of 230 grams of dried copra meal using analytical balance; then place it
in the blender and grind the 4 sets for 8 minutes, one set will serve as the control.
2. Sieve each set of ground copra meal using Mesh 24, 32 42, and 60, then weigh the
recovered ground copra meal.
3. Place the ground copra meal in the beaker, then add 460mL of isopropanol. Heat in
a hot plate for 15minutes at 50°C, then weigh the defatted copra meal.
4. Calculate the oil removed by subtracting the defatted copra meal from ground copra
meal.
B-5. Analysis
As shown in Table 3.10, the mesh size of the copra meal is indirectly proportional to
the amount of oil removed. Highest amount of oil was removed at mesh 60 (0.250mm),
yielding an oil removal thrice of that of the control (dried copra meal). Furthermore, it was
observed that the control yields low oil removal due to its low surface area for reaction and
inability to completely mix with the solvent. This also justifies that grinding of dried copra meal
is necessary for more effective oil removal.
B-6. Conclusion
The optimum size of copra meal is mesh 60 (0.250mm).
B-1. Objective
To determine the optimum grinding time of dried copra meal that would yield the
highest percentage recovery when passed through Tyler Mesh 60 (0.250mm) sieve.
B-2. Hypothesis
Longer grinding time would result to smaller particle size of copra meal, thus majority
of the dried copra meal will pass through Mesh 60 (0.250mm) at 10 minutes of grinding.
B-3. Procedure
1. Weigh 5 sets of 230 grams of dried copra meal using analytical balance; then place it
in the blender and grind each set for 2, 4 6, 8 and 10 minutes.
2. Sieve the ground copra meal using Tyler Mesh 60 (0.250mm) and record the weight
of the ground copra meal that passed through the sieve.
226𝑔
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑌𝑖𝑒𝑙𝑑 (%) = ∗ 100
230𝑔
B-6. Analysis
As shown in Table 3.11, the mass of copra meal that passed through 0.250 mm sieve
increases as the time of grinding also increases. At 8 minutes grinding, 98.26% of copra meal
was recovered, however minimal increment was observed in the succeeding minutes of
grinding.
B-7. Conclusion
Several parameters such as solvent type, ratio of defatted copra meal to solvent,
operating temperature and time were varied to achieve high oil removal. Furthermore, the
selection of optimum parameter will be based on the percent of oil removed using the formula:
𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑖𝑙 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 (𝑔)
𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑜𝑖𝑙 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 (%) = ∗ 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑖𝑙 (𝑔)
The actual mass is the amount of oil that was removed during the experiment, while
the theoretical mass is the maximum amount of oil that could be removed. The higher the
percent oil removed, the better the reaction.
Laboratory Set-up
To determine the optimum type of solvent that would give the highest oil percent
removal in leaching of copra meal.
A-2. Hypothesis
The best solvent is hexane.
A-3. Procedure
1. Weigh 226g ground copra meal and 452mL chloroform, then place them in 1L
beaker covered with foil.
2. Heat the beaker in a hotplate for 50°C for 15min, then filter the mixture using filter
paper and funnel.
3. Weigh and record the mass of defatted copra meal and the spent solvent.
4. Repeat steps 1-3 using different solvents: acetone, petroleum ether, isopropanol,
and hexane.
From Table 3.12, it shows that highest oil removed was obtained using isopropanol
and acetone among other solvents. However, during the reaction, almost half of the acetone
was not recovered, because its boiling point (56°C) is close to the operating temperature of
50°C, causing the solvent to vaporize. Same trend was also observed in using petroleum
ether since its boiling point is 47°C. On the other hand, isopropanol has high boiling point of
82.6°C, which explains the minimal solvent loss.
A-7. Conclusion
B-2. Hypothesis
A ratio of 1 part ground copra meal to 5 parts solvent (w/v) is optimal.
B-3. Procedure
1. Weigh 226g ground copra meal and 226mL isopropanol, then place them in 2L beaker
covered with foil.
2. Heat the beaker in a hotplate for 50°C for 15min, then filter the mixture using filter
paper and funnel.
3. Weigh and record the mass of defatted copra meal. Then repeat steps 1-2 using
different amount of isopropanol: 452mL, 678mL, 904mL, and 1130mL.
B-6. Analysis
From Table 3.13, it shows that the ratio of the ground copra meal to solvent is directly
proportional to the percent of oil removed. At 1:3 (w/v), high amount of oil was removed,
however succeeding ratios of 1:4 and 1:5 led to a minimal increment of oil removal. On the
other hand, it was observed that lower ratios led to a more viscous mixture, making it difficult
to mix.
B-7. Conclusion
C-1. Objective
To determine the optimum temperature for leaching that would give the highest oil
percent removal.
C-2. Hypothesis
Higher temperature of leaching would result to higher percentage oil removal, thus
70°C would be the optimum temperature.
C-3. Procedure
1. Weigh 226g ground copra meal and 678mL isopropanol, then place them in 1L beaker
covered with foil.
2. Heat the beaker in a hotplate for 40°C for 15min, then filter the mixture using filter
paper and funnel.
3. Weigh and record the mass of defatted copra meal. Then repeat steps 1-2 using
different leaching temperatures: 50°C, 60°C, 70°C and 80°C
From Table 3.14, it was observed that increasing the operating temperature led to
more oil removed from the copra meal. Highest oil removal was recorded at 80°C, however
it was observed during the experiment that solvent recovery is low since it is close to the
boiling point of isopropanol. Moreover, the researchers decided to select 70°C since there is
only a minimal increment between the oil removal of 70 and 80°C.
C-7. Conclusion
D-1. Objective
To determine the optimum time for leaching that would give the highest oil percent
removal.
D-2. Hypothesis
Higher time of leaching would result to higher percentage yield, thus 75min would be
the optimum yield.
D-3. Procedure
1. Weigh 226g ground copra meal and 678mL isopropanol, then place them in 1L
beaker covered with foil.
2. Heat the beaker in a hotplate for 70°C for 15min, then filter the mixture using filter
paper and funnel.
3. Determine and record the mass of defatted copra meal and spent solvent.
4. Repeat steps 1-3 using different leaching time: 30min, 45min, 60min, and 75min
D-4. Data and Results
Table 3.15. Determination of Optimum Time for Leaching
Trial 1 2 3 4 5
Mass of Ground
226 226 226 226 226
Copra Meal (g)
Type of Solvent Isopropanol Isopropanol Isopropanol Isopropanol Isopropanol
Ratio of Ground
CM to Solvent 1:3 1:3 1:3 1:3 1:3
(w/v)
Volume of Solvent
678 678 678 678 678
(mL)
Temperature (°C) 70 70 70 70 70
Time (min) 15 30 45 60 75
Mass of Defatted
211 209 208 206 206
Copra Meal (g)
Mass of Oil
15 17 18 20 20
Removed (g)
Percent Oil
64.52 73.12 77.42 86.02 86.02
Removed (%)
As shown in Table 3.15, there was a direct proportionality between the operating time
and the percent of oil removed. At 60 minutes of leaching, oil removed reached 20 grams
(86.02% yield), however further leaching to 75 minutes did not have significant difference.
D-7. Conclusion
Figure 3.13. Laboratory Set-up for Oil Content of Defatted Copra Meal Determination
E-3. Objective
To determine the oil content of defatted copra meal in order to justify the oil removal
through leaching.
E-4. Hypothesis
The oil content of defatted copra meal would be less than 2%.
E-5. Procedure
1. Weigh 206grams defatted copra meal and 500mL isopropanol, then place them in the
soxhlet extractor and round bottom flask, respectively. Prepare the set-up as shown in
Figure 3.13.
2. Set the hotplate at 90°C to reflux, and turn on the pump to allow the flow of water in
the condenser.
3. After 4 hours, determine the mass of recovered oil by vaporizing the solvent in the
round bottom flask.
Table 3.16. Determination of Oil Content of Defatted Copra Meal through Soxhlet Apparatus
Mass of Defatted Copra Meal (g) 206
Volume of Isopropanol (mL) 500
Mass of Oil Obtained (g) 2
Percent Oil Content (%) 0.97
E-8. Analysis
In the study, the initial oil content of copra meal of 9.3% was reduced to 0.97% through
leaching using isopropanol at 1:3 (w/v) ratio. This proves that significant amount of residual
oil was removed at 70°C reaction for 60 minutes.
E-9. Conclusion
The mass of total extractable mannose is first calculated as 51% of the starting mass
of ground copra meal (Saittagaroon, 2006). The formula for total extractable mannose is,
Figure 3.15. Benedict’s Reagent Before and After Reacting with Reducing Sugars
The reaction mechanism shown in Figure 3.15, indicates that a mole of precipitated
cupric oxide (Cu2O) is equivalent to a mole of reducing sugar. This means that the amount of
reducing sugar in the solution can be determined indirectly by stoichiometry
In order to determine the amount of reducing sugars after each hydrolysis trials, 1mL
of sample hydrolysate (supernatant) was collected and reacted with 5mL of Benedict’s
Reagent. After reaction, the precipitated cupric oxide is filtered, washed, dried, and weighed.
The amount of mannose in the sample is then calculated as
Figure 3.17. Laboratory Set-up for Acid Hydrolysis of Defatted Copra Meal
A-2. Hypothesis
The optimum acid type to use is hydrochloric acid.
A-3. Procedure
1. Weigh 3 sets of 206g defatted copra meal and prepare 824mL of 1.80% w/w
hydrochloric acid, then place it in the 3-neck round bottom flask.
2. Put the 3-neck round bottom flask to the hotplate and set to 100°C for 30 minutes.
3. Afterwards, filter the mixture using funnel and filter paper, then measure the
hydrolysate solution (liquid) obtained.
4. Determine the concentration of mannose in the hydrolysate solution using Benedict ’s
reagent.
5. Repeat the steps 1-4 using different acid type such as sulfuric and phosphoric acid.
79.17𝑔
%𝑦𝑖𝑒𝑙𝑑 =
105.06𝑔
%𝒚𝒊𝒆𝒍𝒅 = 𝟕𝟓. 𝟑𝟔%
A-6. Analysis
The highest percent yield of mannose is obtained using phosphoric acid at 75.36%
compared to the 68.30 and 70.54% of sulfuric and hydrochloric acid respectively. This is
attributed to phosphoric acid being a triprotic acid or an acid with 3 protonating hydrogens,
which attacks beta glycosidic bonds holding the mannose together in a more aggressive
manner.
A-7. Conclusion
The optimum acid type to use in hydrolysis, which extracted the highest amount of
mannose (79.17g) with a percent yield of 75.36%, is phosphoric acid.
B-2. Hypothesis
The optimum acid concentration is between 2.0-3.0 (%w/w)
B-3. Procedure
1. Weigh 5 sets of 206g defatted copra meal and prepare 824mL of 0.20% w/w
phosphoric acid, then place it in the 3-neck round bottom flask.
2. Put the 3-neck round bottom flask to the hotplate and set to 100°C for 30 minutes.
3. Afterwards, filter the mixture using funnel and filter paper, then measure the
hydrolysate solution (liquid) obtained.
4. Determine the concentration of mannose in the hydrolysate using Benedict ’s reagent.
5. Repeat the steps 1-4 using different concentration such as 1.0, 1.8, 2.6, 3.4% w/w
phosphoric acid.
B-4. Data and Results
Table 3.18. Determination of Optimum Acid Concentration for Hydrolysis
TRIAL 1 2 3 4 5
Type of Acid Phosphoric Phosphoric Phosphoric Phosphoric Phosphoric
Mass of Defatted CM (g) 206 206 206 206 206
Concentration of Acid
0.20 1.00 1.80 2.60 3.40
(% w/w)
Ratio of Defatted CM to
1:4 1:4 1:4 1:4 1:4
Acid
Temperature (°C) 100°C 100°C 100°C 100°C 100°C
Time (min) 30 30 30 30 30
Volume of Hydrolysate
789 790 779 784 788
(mL)
Mass of Red Cu2O
Precipitate per mL of 0.0476 0.0626 0.0789 0.0892 0.0908
hydrolysate (g)
Mass of Mannose (g) 47.28 62.26 77.38 88.05 90.08
% Yield 45.00 59.26 73.65 83.81 85.74
88.0475𝑔
%𝑦𝑖𝑒𝑙𝑑 =
105.06𝑔
B-6. Analysis
The highest percent yield (83.81%) of mannose is obtained using 2.60% w/v
phosphoric acid. The succeeding variation of 3.40% w/v phosphoric acid has a higher percent
yield (85.74%), however, the difference of mannose extracted is not significantly greater.
Thus, the optimal acid concentration was determined to be 2.60% w/v phosphoric.
B-7. Conclusion
C-2. Hypothesis
Higher ratio would result to higher yield, thus the optimal ratio is 1:10.
C-3. Procedure
1. Weigh 5 sets of 206g defatted copra meal and prepare 824mL of 2.60% w/w
phosphoric acid (1:4 ratio), then place it in the 3-neck round bottom flask.
2. Put the 3-neck round bottom flask to the hotplate and set to 100°C for 30 minutes.
3. Afterwards, filter the mixture using funnel and filter paper, then measure the
hydrolysate solution (liquid) obtained.
4. Determine the concentration of mannose in the hydrolysate using Benedict ’s reagent.
5. Repeat the steps 1-4 using different ratio such as 1:6, 1:8, 1:10, 1:12 (%m/w).
C-4. Data and Results
Table 3.19. Determination of Optimum Ratio of Copra Meal to Acid for Hydrolysis
TRIAL 1 2 3 4 5
Type of Acid Phosphoric Phosphoric Phosphoric Phosphoric Phosphoric
Mass of Defatted CM (g) 206 206 206 206 206
Concentration of Acid
2.60 2.60 2.60 2.60 2.60
(% w/w)
Ratio of Defatted CM to
1:4 1:6 1:8 1:10 1:12
Acid
Temperature (°C) 100°C 100°C 100°C 100°C 100°C
Time (min) 30 30 30 30 30
Volume of Hydrolysate
785 1185 1550 1953 2398
(mL)
Mass of Red Cu2O
Precipitate per mL of 0.0885 0.0602 0.0472 0.0376 0.0308
hydrolysate (g)
Mass of Mannose (g) 87.47 89.82 92.11 94.45 92.99
% Yield 83.26 81.69 87.67 89.90 85.51
92.1103𝑔
%𝑦𝑖𝑒𝑙𝑑 =
105.06𝑔
C-6. Analysis
Starting from the third trial with a mass to volume ratio of 1:8, there was no significant
increase in concentration of mannose, with increasing mass to volume ratios as shown in the
data. The third trial extracted 92.11g of mannose which represents a percent yield of 87.67%
Thus, the optimal mass to volume ratio of copra meal to acid was determined to be 1:8.
C-7. Conclusion
The optimum mass to volume ratio of copra meal to acid to use in hydrolysis, which
extracted 92.11g of mannose with a percent yield of 87.67%, is 1:8.
D-2. Hypothesis
The optimum temperature for hydrolysis is 100°C
D-3. Procedure
1. Weigh 5 sets of 206g defatted copra meal and prepare 1648mL of 2.60% w/w
phosphoric acid, then place it in the 3-neck round bottom flask.
2. Put the 3-neck round bottom flask to the hotplate and set to 80°C for 30 minutes.
3. Afterwards, filter the mixture using funnel and filter paper, then measure the
hydrolysate solution (liquid) obtained.
4. Determine the concentration of mannose in the hydrolysate using Benedict ’s reagent.
5. Repeat the steps 1-4 using different temperature such as 90, 100, 110, 120°C
D-4. Data and Results
Table 3.20. Determination of Optimum Temperature for Acid Hydrolysis
TRIAL 1 2 3 4 5
Type of Acid Phosphoric Phosphoric Phosphoric Phosphoric Phosphoric
Mass of Defatted CM (g) 206 206 206 206 206
Concentration of Acid
2.60 2.60 2.60 2.60 2.60
(% w/w)
Ratio of Defatted CM to
1:8 1:8 1:8 1:8 1:8
Acid
Temperature (°C) 80°C 90°C 100°C 110°C 120°C
Time (min) 30 30 30 30 30
Volume of Hydrolysate
1555 1562 1570 - -
(mL)
Mass of Red Cu2O
Precipitate per mL of 0.0364 0.0405 0.0470 - -
hydrolysate (g)
Mass of Mannose (g) 71.26 79.64 92.90 - -
% Yield 67.83 75.79 88.43 - -
92.9032𝑔
%𝑦𝑖𝑒𝑙𝑑 =
105.06𝑔
%𝒚𝒊𝒆𝒍𝒅 = 𝟖𝟖. 𝟒𝟑%
D-6. Analysis
No data were collected at trials 4 and 5 with temperatures 110 and 120°C respectively
as the temperature of the solution did not rise more than 102°C despite setting the hot plate
at higher temperatures. Thus, the optimal temperature to use is 100°C which extracted
92.90g of mannose, representing a percent yield of 88.43%
D-7. Conclusion
The optimum temperature for acid hydrolysis is 100°C, which extracted 92.90g of
mannose with a percent yield of 88.43%.
E-2. Hypothesis
The optimum time for hydrolysis to use is 60 minutes.
E-3. Procedure
1. Weigh 5 sets of 206g defatted copra meal and prepare 1648mL of 2.60% w/w
phosphoric acid, then place it in the 3-neck round bottom flask.
2. Put the 3-neck round bottom flask to the hotplate and set to 100°C for 30 minutes.
3. Afterwards, filter the mixture using funnel and filter paper, then measure the
hydrolysate solution (liquid) obtained.
4. Determine the concentration of mannose in the hydrolysate using Benedict ’s reagent.
5. Repeat the steps 1-4 using different time such as 60, 90, 120, 150 minutes.
E-4. Data and Results
Table 3.21 Determination of Optimum Time for Acid Hydrolysis
TRIAL 1 2 3 4 5
Type of Acid Phosphoric Phosphoric Phosphoric Phosphoric Phosphoric
Mass of Defatted CM (g) 206 206 206 206 206
Concentration of Acid
2.60 2.60 2.60 2.60 2.60
(% w/w)
Ratio of Defatted CM to
1:8 1:8 1:8 1:8 1:8
Acid
Temperature (°C) 100°C 100°C 100°C 100°C 100°C
Time (min) 30 60 90 120 150
Volume of Hydrolysate
1558 1552 1560 1548 1561
(mL)
Mass of Red Cu2O
Precipitate per mL of 0.0475 0.0492 0.0512 0.0473 0.0418
hydrolysate (g)
Mass of Mannose (g) 93.17 96.14 100.56 92.19 82.15
% Yield 88.68 91.51 95.72 87.50 78.19
100.5607𝑔
%𝑦𝑖𝑒𝑙𝑑 =
105.06𝑔
E-6. Analysis
E-7. Conclusion
The optimum reaction time for acid hydrolysis is 90 min which extracted 100.56g of
mannose representing a 95.72% yield
III-2. Neutralization
Laboratory Set-up
A-2. Hypothesis
The optimum type of neutralizing agent is calcium hydroxide.
A-3. Procedure
1. Weigh 5 grams of sodium carbonate and prepare 100g of hydrolysate, then place them
in a beaker.
2. Put the beaker in a hotplate under stirring at room temperature for 10 minutes then
record the pH.
3. Repeat the procedure by using calcium hydroxide and potassium hydroxide as the
neutralizing agent.
A-4. Data and Results
Table 3.22. Determination of Optimum Type of Neutralizing Agent
Trial 1 2 3
Type of Neutralizing Agent Sodium Carbonate Calcium Hydroxide Potassium Hydroxide
Mass of Hydrolysate (g) 100 100 100
pH before treatment 1.6 1.6 1.6
pH after treatment 6.5 3.3 8.9
The precipitate
No precipitate No precipitate
calcium phosphate
Observation formed during the formed during the
is insoluble to the
reaction reaction
solution
A-5. Analysis
Based on Table 3.21, addition of sodium carbonate, calcium hydroxide and potassium
hydroxide increased the pH of the hydrolysate from 0.6 to 6.5, 3.4 and 8.9 respectively.
However, the salt formed during the neutralization with sodium carbonate and potassium
hydroxide as the neutralizing agent, is soluble to the solution. On the other hand, the salt
formed in the second trial was found to be insoluble to the solution and can be separated
through filtration process Thus, the selected neutralizing agent in this process is calcium
hydroxide
A-6. Conclusion
The optimum type of neutralizing agent for the neutralization of the hydrolysate is
calcium hydroxide.
B-1 Objective
To determine the amount of neutralizing agent that would give a pH ranging from 4.6
to 4.8.
B-2. Hypothesis
The amount of calcium carbonate that will raise the pH to 4.7 will be greater than 5
grams.
B-3. Procedure
1. Weigh 5 grams and prepare another five to ten sets of 1 gram of calcium hydroxide.
2. Add each set of calcium hydroxide to the hydrolysate and record the corresponding
change in pH.
3. Stop the addition of calcium hydroxide when it reached the desired pH
4. Filter the mixture and record the mass of the neutralized and filtered hydrolysate
(mannose).
5. Calculate the percent yield.
B-6. Analysis
Based on the table, the neutralized hydrolysate reached the desired pH of 4.7 after
the addition of 10 g calcium hydroxide. Additionally, the recorded mass of cake or the
precipitate calcium phosphate during the neutralization process was found to be almost equal
to the theoretical yield of 13.9541 g, resulting to a 93.16% yield.
Additionally, the amount of mannose present in the neutralized hydrolysate was again
determined using Benedict’s Quantitative Test. The amount of mannose in 96g (99.84mL) of
neutralized hydrolysate is found to be 5.68g.
Lastly, only a representative sample was neutralized out of the total amount of 170.6g
(1560mL) of hydrolysate. Thus, the actual amount of Ca(OH)2 to be used is calculated as
170.6g. Similarly, the actual amount of mannose in is calculated to be 100.94g in 1638g of
solution
B-7. Conclusion
The amount of neutralizing agent, calcium hydroxide, required during the neutralization
process is 170.6g.
III-3. Reduction
Reduction of the aldehyde group of mannose yields its sugar alcohol counterpart,
mannitol (Rastogi, S.C., 2003). The reduction mechanism of mannose to mannitol is shown
in Figure 2.6.
𝒎 𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
%𝒚𝒊𝒆𝒍𝒅 = × 𝟏𝟎𝟎%
𝒎 𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
Laboratory Set-up
A-2. Hypothesis
The optimum molar ratio of mannose to sodium borohydride is 1:1
A-3. Procedure
1. Weigh 5 sets of 1638g of mannose solution in a beaker.
2. For a molar ratio of 1:0.50, add 10.57g of sodium borohydride to the mannose solution
and react the mixture for 30 mins at room temperature (25°C).
3. Crystallize and weigh the mannitol obtained.
4. Replicate the procedure for molar ratios 1:0.75, 1:1, 1:1.25. 1:1.50
The amount of sodium borohydride to be added for a molar ratio of 1:1.25 is calculated as,
𝒎 𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
%𝒚𝒊𝒆𝒍𝒅 =
𝒎 𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
54𝑔
%𝑦𝑖𝑒𝑙𝑑 = × 100%
102.0695𝑔
A-7. Conclusion
The optimal molar ratio of mannose to sodium borohydride is 1:1.25 with a percent
yield of 52.91%.
B-2. Hypothesis
The optimum temperature is 30°C
B-3. Procedure
1. Weigh 5 sets of 1638g of mannose solution in a beaker.
2. Add 26.50g of sodium borohydride to the mannose solution and react the mixture for
30 mins at room temperature (25°C).
3. Crystallize and weigh the mannitol obtained.
4. Replicate the procedure for temperatures 30, 40, 50, 60°C
TRIAL 1 2 3 4 5
Mass of
100.94 100.94 100.94 100.94 100.94
Mannose (g)
Molar Ratio (mol
mannose: mol 1:1.25 1:1.25 1:1.25 1:1.25 1:1.25
NaBH4)
Mass of NaBH4
26.50 26.50 26.50 26.50 26.50
(g)
Temperature
25 30 40 50 60
(°C)
Time (min) 30 30 30 30 30
Mass of
60 58 58 56 54
Mannitol (g)
% Yield (%) 58.78 56.82 56.82 54.86 52.91
𝒎 𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
%𝒚𝒊𝒆𝒍𝒅 =
𝒎 𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
60𝑔
%𝑦𝑖𝑒𝑙𝑑 = × 100%
102.0695𝑔
The highest percent yield of mannitol is obtained using a reaction temperature of 25°C
(trial 1) or room temperature at 58.78%. This is the only trial that required no heating as the
room temperature at the laboratory was nearly 25°C. It was observed that there was slight
decline in the amount of recovered mannitol as the reaction temperature was increased. This
is attributed to the instability of sodium borohydride in water at room temperature alone, much
more at elevated temperatures. (Martelli et al, 2010)
B-7. Conclusion
C-2. Hypothesis
The optimum reduction time is 120 minutes
C-3. Procedure
1. Weigh 5 sets of 1638g of mannose solution in a beaker.
2. Add 26.50g of sodium borohydride to the mannose solution and react the mixture for
30 mins at room temperature (25°C).
3. Crystallize and weigh the mannitol obtained.
4. Replicate the procedure for times 60, 90, 120, and 150 minutes
𝒎 𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
%𝒚𝒊𝒆𝒍𝒅 =
𝒎 𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒎𝒂𝒏𝒏𝒊𝒕𝒐𝒍
89𝑔
%𝑦𝑖𝑒𝑙𝑑 = × 100%
100.0695𝑔
C-6. Analysis
The highest percent yield of mannitol is obtained using reaction times 120 and 150
minutes, both at 89.15%. Looking at the preceding trial (3), however, a comparable yield was
also attained at 87.20%. It was observed that the reaction did not proceed beyond 90
minutes. Thus, the third trial was selected as the optimum.
Additionally, the volume of the optimal trial was found to be 1542mL (1645g)
C-7. Conclusion
The optimal reaction time in the reduction of mannose to mannitol is 90 minutes with
a percent yield of 87.20%.
III-4. Evaporation
𝑭=𝑽+𝑪
Conducting a solute balance,
𝑭(0.0577) = 𝑪(0.20)
(1645𝑔)(0.0577) = 𝑪(0.20)
𝑪 = 𝟒𝟕𝟒. 𝟓𝟖𝒈
Substituting known values in the first equation,
𝑭=𝑽+𝑪
1645𝑔 = 𝑽 + 474.58𝑔
𝑽 = 𝟏𝟏𝟕𝟎. 𝟒𝟐𝒈
The material balance indicates that for a feed of 1645g solution at 5.77%
concentration, 1170.42g of water must be evaporated to increase the concentration to 20%.
Laboratory Set-up
A-2. Hypothesis
A-3. Procedure
89𝑔 𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙
𝐶𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 (%) = × 100%
𝑉𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
89𝑔 𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙
𝐶𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = × 100%
(𝑚𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 )(𝜌𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 )−1
89𝑔 𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙
𝐶𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = × 100%
𝑔 −1
(471𝑔) (1.0467 𝑚𝐿)
A-6. Analysis
It was observed that at 140 minutes of evaporation, 1174g of water was already
evaporated which is close to the theoretical value of 1170g calculated using material balance.
This gives a final concentration of mannitol at 19.79% which is very close to the desired
concentration of 20%
A-7. Conclusion
IV. Esterification
Alkyd resins are organic polyesters derived from a polyhydric alcohol and a polybasic
acid. In this study, mannitol is the polyhydric alcohol and phthalic anhydride is the polybasic
acid to be used. When a hydroxyl group of mannitol reacts with a carboxylic acid group of
phthalic anhydride, an ester is formed. Water is the by-product of this reaction, hence, it is
sometimes referred to as a condensation reaction.
The esterification reaction shown in Figure 2.8 is reversible, thus, water must be
removed in order to shift the reaction and favor the formation of esters. As the equation
shows, the reaction takes place between the hydroxyl group of the alcohol and the carboxyl
group of the acid (Elliott, 1993).
Parameters such as molar ratios of the reactants, reaction temperature, and reaction
time were considered in this study. The optimum parameters were chosen based on the acid
value of the alkyd resin after the reaction. The acid value is technically defined as the number
of milligrams of potassium hydroxide (KOH) required to neutralize one gram of sample under
a set of specified conditions. The acid value also determines the extent of reaction, where a
smaller value dictates a more complete esterification reaction. The acid value determination
was based on the formulas and methods of analysis provided by the International Union of
Pure and Applied Chemistry (IUPAC). The acid value and is calculated as:
𝒂𝑵
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟔. 𝟏 ( )
𝒑
The yield is simple taken as the quotient of the final mass and the initial mass. The yield is
calculated as,
𝒎𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝒚𝒊𝒆𝒍𝒅 (%) = × 𝟏𝟎𝟎%
𝒎𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
Laboratory Set-up
Figure 3.31. Laboratory Set-up for Esterification Figure 3.32. Production of Alkyd Resin
A-3. Procedure
1. Weigh 5 sets of 471g concentrated mannitol solution in a beaker.
2. For a molar ratio of 1:1:1 of mannitol to phthalic anhydride to palmitic acid, add 72.33g
of phthalic anhydride and 125.25g of palmitic acid to the beaker.
3. React the mixture at 240°C for 1 hour then measure the acid value.
4. Replicate the procedure using benzoic and oleic acids as modifier.
Appearance
From the previous process, the concentration mannitol and density of solution were
determined. Substituting these values to the above equation,
𝑔 −1
𝑚𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = (0.1977) (471𝑔 × 1.0467 )
𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
The acid value for a resin sample of 0.8962g requiring 628mL of 0.1374N KOH is calculated as,
𝒂𝑵
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟔. 𝟏 ( )
𝒑
(628𝑚𝐿)(0.1374𝑁)
𝑎𝑐𝑖𝑑 𝑣𝑎𝑙𝑢𝑒 = 56.1 [ ]
0.8962𝑔
𝒎𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝒚𝒊𝒆𝒍𝒅 (%) = × 𝟏𝟎𝟎%
𝒎𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
290𝑔
𝑦𝑖𝑒𝑙𝑑 (%) = × 100%
(89.96 + 72.33 + 137.97)𝑔
A-6. Analysis
Oleic acid as a modifier gave a clear liquid product as compared to the cloudy liquid
that stearic acid and clear solid that benzoic acid yielded. Besides the appearance, oleic acid
as a modifier gave the lowest number of acid value. Acid value is an indicator of how complete
the esterification reaction is, where a lower value represents a more complete reaction.
Comparing the three modifiers based on the appearance of the product obtained
In terms of the yield, all three modifiers are uniform at 96.33, 95.08, and 96.58%.
Nevertheless, oleic acid modifier gave the highest yield at 96.58%
A-7. Conclusion
The optimal alkyd resin modifier type is oleic acid with the lowest acid value at 5401.37
mgKOH and a percent yield of 96.58%.
B. Determination of the Optimal Molar Ratio of Mannitol to Phthalic Anhydride to Oleic Acid
B-1. Objective
To determine the optimal molar ratio of mannitol to phthalic anhydride to oleic acid
that would yield high amount of alkyd resin with low acid value.
B-2. Hypothesis
The optimal modifier to use is 1:1:1
B-3. Procedure
1. Weigh 5 sets of 471g concentrated mannitol solution in a beaker.
2. For a molar ratio of 1:1:1 of mannitol to phthalic anhydride to oleic acid, add 72.33g
of phthalic anhydride and 137.97g of oleic acid to the beaker.
3. React the mixture at 240°C for 1 hour then measure the acid value.
4. Replicate the procedure using ratios, 1:1:2, 1:1:3, 1:2:1, and 1:3:1
Table 3.29 Determination of the Optimal Molar Ratio of Mannitol to Phthalic Anhydride to Oleic Acid
TRIAL 1 2 3 4 5
Mass of Mannitol in
89.96 89.96 89.96 89.96 89.96
Solution (g)
Molar Ratio
(mol mannitol: mol
1:1:1 1:1:2 1:1:3 1:2:1 1:3:1
phthalic anhydride:
mol modifier)
Mass of Phthalic
72.33 72.33 72.33 144.66 216.99
Anhydride (g)
Mass of Oleic Acid
137.97 275.94 413.91 137.97 137.97
(g)
Temperature (°C) 240°C 240°C 240°C 240°C 240°C
Time (min) 60 60 60 60 60
Mass of Alkyd Resin
287 411 531 342 425
(g)
Acid Value (mgKOH) 5321.12 8540.15 11567.21 7985.14 10987.02
Cloudy Cloudy
Appearance Clear liquid Clear solid Clear liquid
liquid liquid
Yield (%) 95.58 93.79 92.64 91.79 95.52
From the previous process, the concentration mannitol and density of solution were
determined. Substituting these values to the above equation,
𝑔 −1
𝑚𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = (0.1977) (471𝑔 × 1.0467 )
𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
The acid value for a resin sample of 0.7214g requiring 498mL of 0.1374N KOH is calculated as,
𝒂𝑵
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟔. 𝟏 ( )
𝒑
(498𝑚𝐿)(0.1374𝑁)
𝑎𝑐𝑖𝑑 𝑣𝑎𝑙𝑢𝑒 = 56.1 [ ]
0.7214𝑔
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟑𝟐𝟏. 𝟏𝟏𝟔𝟗 𝒎𝒈𝑲𝑶𝑯
Finally, the yield is calculated as,
𝒎𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝒚𝒊𝒆𝒍𝒅 (%) = × 𝟏𝟎𝟎%
𝒎𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
287𝑔
𝑦𝑖𝑒𝑙𝑑 (%) = × 100%
(89.96 + 72.33 + 137.97)𝑔
B-6. Analysis
Based on the appearance of the products, trials 4 and 5 did not conform to the
standard and existing product which is a clear liquid. Trials 1, 2, and 3 yielded a clear liquid,
however, first trial gave the lowest acid value indicating that it has a higher extent of reaction
than the other trials. Moreover, trial 1 has the highest percent yield at 95.58%
B-7. Conclusion
The optimal ratio of mannitol to phthalic anhydride to oleic acid is 1:1:1 which gave
the lowest acid value and a percent yield of 95.58%
C-3. Procedure
1. Weigh 5 sets of 471g concentrated mannitol solution in a beaker.
2. For a molar ratio of 1:1:1 of mannitol to phthalic anhydride to oleic acid, add 72.33g
of phthalic anhydride and 137.97g of oleic acid to the beaker.
3. React the mixture at 220°C for 1 hour then measure the acid value.
4. Replicate the procedure using temperatures 230, 240, 250, 260°C
From the previous process, the concentration mannitol and density of solution were
determined. Substituting these values to the above equation,
𝑔 −1
𝑚𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = (0.1977) (471𝑔 × 1.0467 )
𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
The acid value for a resin sample of 0.8214g requiring 562mL of 0.1374N KOH is calculated as,
𝒂𝑵
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟔. 𝟏 ( )
𝒑
(562𝑚𝐿)(0.1374𝑁)
𝑎𝑐𝑖𝑑 𝑣𝑎𝑙𝑢𝑒 = 56.1 [ ]
0.8214𝑔
𝒎𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝒚𝒊𝒆𝒍𝒅 (%) = × 𝟏𝟎𝟎%
𝒎𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
285𝑔
𝑦𝑖𝑒𝑙𝑑 (%) = × 100%
(89.96 + 72.33 + 137.97)𝑔
C-6. Analysis
Based on the appearance of the products, trials 4 and 5 did not conform to the
standard and existing product which is of light brown to amber in color. Trials 4 and 5 are
darker in color than the existing product attributed to high reaction temperature. Trials 1 and
2 yielded a clear liquid but are light in color, attributed to low reaction temperatures. Trial 3
yielded a clear amber liquid similar to the existing product.
Although trials 4 and 5 gave a lower acid value than trial 3, it was eliminated
considering its appearance. Considering the first three trials, trial 3 has the lowest acid value
and has more resemblance with the existing product in terms of color.
C-7. Conclusion
The optimal temperature of esterification is 240°C which yielded a clear amber liquid
with a percent yield of 94.92%
D-3. Procedure
1. Weigh 5 sets of 471g concentrated mannitol solution in a beaker.
2. For a molar ratio of 1:1:1 of mannitol to phthalic anhydride to oleic acid, add 72.33g
of phthalic anhydride and 137.97g of oleic acid to the beaker.
3. React the mixture at 240°C for 60 minutes then measure the acid value.
4. Replicate the procedure using times 120, 180, 240, 300 minutes
TRIAL 1 2 3 4 5
Mass of Mannitol in
89.96 89.96 89.96 89.96 89.96
Solution (g)
Molar Ratio
(mol mannitol: mol
1:1:1 1:1:1 1:1:1 1:1:1 1:1:1
phthalic anhydride:
mol modifier)
Mass of Phthalic
72.33 72.33 72.33 72.33 72.33
Anhydride (g)
Mass of Oleic Acid
137.97 137.97 137.97 137.97 137.97
(g)
Temperature (°C) 240°C 240°C 240°C 240°C 240°C
Time (min) 60 120 180 240 300
Mass of Alkyd Resin
282 284 285 287 288
(g)
Acid Value (mgKOH) 5293.14 798.28 102.98 9.56 7.14
Amber clear Amber clear Amber clear Amber clear Brown clear
Appearance
liquid liquid liquid liquid liquid
Yield (%) 93.92 94.58 94.92 95.58 95.92
From the previous process, the concentration mannitol and density of solution were
determined. Substituting these values to the above equation,
𝑔 −1
𝑚𝑚𝑎𝑛𝑛𝑖𝑡𝑜𝑙 = (0.1977) (471𝑔 × 1.0467 )
𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
The acid value for a resin sample of 5.2436 requiring 6.5mL of 0.1374N KOH is calculated as,
𝒂𝑵
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟓𝟔. 𝟏 ( )
𝒑
(6.5𝑚𝐿)(0.1374𝑁)
𝑎𝑐𝑖𝑑 𝑣𝑎𝑙𝑢𝑒 = 56.1 [ ]
5.2436𝑔
𝒂𝒄𝒊𝒅 𝒗𝒂𝒍𝒖𝒆 = 𝟗. 𝟓𝟓𝟓𝟏 𝒎𝒈𝑲𝑶𝑯
Finally, the yield is calculated as,
𝒎𝒑𝒓𝒐𝒅𝒖𝒄𝒕
𝒚𝒊𝒆𝒍𝒅 (%) = × 𝟏𝟎𝟎%
𝒎𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
287𝑔
𝑦𝑖𝑒𝑙𝑑 (%) = × 100%
(89.96 + 72.33 + 137.97)𝑔
𝒚𝒊𝒆𝒍𝒅 (%) = 𝟗𝟓. 𝟓𝟖%
D-6. Analysis
Based on the data, it was observed that the acid value drastically decreased with an
increase in reaction time. The acid values of trials 4 and 5 are the lowest, indicating that the
esterification is almost complete. However, trial 5 with a reaction time of 300 minutes yielded
a clear liquid that is significantly darker than the existing product. Additionally, the acid value
of trial 4 at 240 minutes is already relatively low.
D-7. Conclusion
The optimal time of esterification is 240 minutes which yielded a clear amber liquid
with a low acid value and a percent yield of 95.58%
Several parameters were varied in each process for optimization. The table below
shows the experimental input and the output in each process, as well as the byproducts
generated.
In order to achieve optimum yield of product, the following operating conditions in each
process should be used as shown in the table below. The optimum parameter values from the
experiment were used in the scaled-up designs in the technical study.
A dry-run, wherein the optimum operating conditions was used, was performed to
determine if there would be significant change in the yield of the intermediate process
materials and the product. The table below shows the amount of input and output in the dry-
run.
The experimental study was done in a laboratory scale. The equivalent industrial
equipment of several laboratory apparatus used in the experiment are listed in the table
below. Moreover, the optimum parameter values from the experiment were used in the scaled-
up designs in the technical study.
A-3. Objective
To determine the bulk density of solid materials in the experiment such as copra meal,
dried copra meal, ground copra meal, defatted copra meal, hydrolyzed cake, and neutralized
cake, and mixtures (ground copra meal-isopropanol mixture, defatted copra meal-acid
mixture, hydrolysate-calcium hydroxide mixture) that will be used in designing handling and
storage equipment.
A-4. Procedure
For defatted copra meal, hydrolyzed cake, and neutralized cake, ground copra meal-
isopropanol mixture, defatted copra meal-acid mixture, hydrolysate-calcium hydroxide
mixture
1. Place and weigh the defatted copra meal in a beaker, and record the volume occupied,
then calculate the bulk density.
2. Repeat the steps using hydrolyzed cake, neutralized cake, ground copra meal-
isopropanol mixture, defatted copra meal-acid mixture and hydrolysate-calcium
hydroxide mixture.
Figure 3.36. Bulk Density of Different Solids and Mixtures in the Experimentation
Trial Mass of Copra Meal (g) Volume Occupied (mL) Bulk Density (g/mL)
1 494 1000 0.494
2 475 1000 0.475
3 499 1000 0.499
4 479 1000 0.479
5 485 1000 0.485
Average 0.486
Trial Mass of Dried Copra Meal (g) Volume Occupied (mL) Bulk Density (g/mL)
1 489 1000 0.489
2 496 1000 0.496
3 505 1000 0.505
4 493 1000 0.493
5 492 1000 0.492
Average 0.495
Trial Mass of Ground Copra Meal (g) Volume Occupied (mL) Bulk Density (g/mL)
1 561 1000 0.561
2 579 1000 0.579
3 572 1000 0.572
4 598 1000 0.598
5 525 1000 0.525
Average 0.567
Solid Mass of Solid (g) Volume Occupied (mL) Bulk Density (g/mL)
Defatted Copra Meal 176 300 0.5867
Hydrolyzed Cake 149 500 0.298
Neutralized Cake 289 350 0.8257
𝑊𝑠 494.00 𝑔 𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝜌𝑏 ) = = = 0.494
𝑉 1000 𝑚𝐿 𝑚𝐿
A-7. Conclusion
The average bulk density of copra meal, ground copra meal, defatted copra meal,
hydrolyzed cake, and neutralized cake are 0.486 g/mL, 0.495 g/mL, and 0.567 g/mL
respectively and the bulk density of defatted copra meal, hydrolyzed cake, neutralized cake,
ground copra meal-isopropanol mixture, defatted copra meal-acid mixture, and hydrolysate-
calcium hydroxide mixture are 0.5867, 0.298, 0.8257, 0.9067, 1.1053, 1.0080g/mL
respectively.
MATERIAL APPARATUS
Spent Isopropanol Analytical Balance
Hydrolysate Pycnometer (50mL)
2.6% Phosphoric Acid
Mannose Solution
Mannitol Solution
Concentrated Mannitol
Alkyd Resin
B-3. Objective
B-4. Procedure
1. Weigh the initial mass of empty 50mL pycnometer; fill the pycnometer with spent
isopropanol then weigh the final mass.
2. Calculate the mass of spent isopropanol by subtracting final to initial mass; then divide
by the volume of 50mL to determine the density.
3. Repeat the steps using hydrolysate, mannose solution, mannitol solution,
concentrated mannitol, and alkyd resin for 3 trials each.
A-7. Conclusion
The density of spent isopropanol, 2.6% (w/v) phosphoric acid, hydrolysate, mannose
solution, mannitol solution, concentrated mannitol, and alkyd resin are 0.8333, 1.06, 1.0933,
1.04, and 1.0467, respectively.
The viscosity of a liquid is a measure of the resistance to flow of one portion of a liquid
past another portion. One of the most frequently used methods of measuring viscosity is the
determination of the time necessary for a given volume of liquid to pass through a length of
capillary tubing. Ostwald viscometer is an example of this type of apparatus.
If 1 , 𝑑1 and 𝑡1 represent the viscosity, density and flow time for liquid under test and
2 , 𝑑2 and 𝑡2 represent the corresponding values for the reference liquid, then
1 𝑑1 𝑡1
=
2 𝑑2 𝑡2
2 𝑑1 𝑡1
1 =
𝑑2 𝑡2
MATERIAL APPARATUS
Phosphoric Acid (2.6%) Ostwald Viscometer
Spent Isopropanol Stopwatch
Hydrolysate Iron clamp
Mannose Solution Iron Stand
Mannitol Solution
Concentrated Mannitol
A-3. Objective
A-4. Procedure
1. Put a certain amount of liquid in the large bulge viscometer and pull it by pipette until
the small bulge is full.
2. Let the liquid to flow through the capillary tube with run time when the liquid reaches
the mark shown on the viscometer and then stopped time when the liquid reaches the
bottom mark. Repeat the experiment and record the results (take average of results).
3. Repeat the experiment to other liquids.
Figure 3.39. Viscosity of Phosphoric Acid (2.6%), Spent Isopropanol, Hydrolysate, Mannose
Solution, Mannitol Solution and Concentrated Mannitol
The peaks represent areas of the spectrum where specific bond vibrations occur. In
the 4000 – 2500 cm-1 region, an element (C or O or N) is detected to have a single bond to
H. Moreover, the rounded peak at 3361.70 cm-1 is attributed to O-H stretching bond
(Sasivardhan, O., 2016). Also, the broader the peak, the more O-H bond is present. On the
other hand, 1650 - 1550 cm-1 region corresponds to double bonded element to C wherein a
sharp peak at 1639.44 cm-1 is attributed to C=O bonding. Lastly, the peak at 1380.29 cm-1
corresponds to C-C bonding. The existence of the three bonds O-H, C=O and C-C proves the
formation of mannose solution during the experiment. This was compared to the IR spectra
obtained from National Institute of Standards and Technology (NIST) shown below. It shows
that the two spectra has the same peaks at 3500-2500cm-1 and 2000-1500 cm-1 regions.
All of the peaks 3399.71, 3288.81, 2967.80, 2947.12, and 2906.66 cm-1 belong to
the 4000 – 2500 cm-1 region. Since the peaks are broad and round, these peaks corresponds
to O-H stretching bonds, meaning it is an alcohol, which is the functional group of mannitol.
This was compared to the IR spectra obtained from National Institute of Standards and
Technology (NIST) shown below. It shows that the two spectra has the same round peaks at
3500-2500cm-1 regions.
As shown above, round peaks at 3411.40 and 2940.37 cm-1 corresponds to O-H
stretching bond. This indicates the unreacted mannitol during esterification. Moreover, the
peak value at 1723.09 cm-1 is attributed to C=O stretching bond, which confirms the presence
of an ester bond in our product. Furthermore, it is close to the values according to Coatings
Technology: Fundamentals, Testing and Processing Techniques of 1730 cm-1.
Esterification of Hydrolyzed Copra (Cocos nucifera) Meal for the Production of Alkyd Resin
Dionisio, C.P., Fulugan, C.L., Redublo, A.P.
PROJECT STUDY 153
PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology
Department of Chemical Engineering