Summary of Experimentation of Hydrothermal Oxidation of Glucose For The Production of Methanoic Acid

Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology

Chemical Engineering Department
INTRODUCTION
Peanut (Arachis hypogaea L.), locally known as mani, is a protein-rich
legume and one of the most popular crops in the Philippines. According to
Bureau of Agricultural Statistics, 29,088.93 metric tons of peanuts has
produced in the year 2013. Peanut is composed of the seed and its shell. Its
shell acts as a protective layer of the seed inside. According to Hill (2009),
whole peanuts contain 20% shell in terms of weight yielding 5,817.79 metric
tons of peanut shells produced in the Philippines. The peanuts shell is mainly
composed of 39.86% a-cellulose, 47.78& lignin, 10.33% moisture, and 2.03%
others (FTUD REPORT No. 044-14, Philippine Fiber Industry Development
Authority, 2015).
These peanut shells are not used in the processing.
Therefore, it is treated as a waste product disposed directly or burned. However,
these peanut shells are lignocellulosic biomass material and can be a
renewable source of a-cellulose for the production of value-added products
such as methanoic acid, which is commonly used in the industries.
Methanoic acid, also known as formic acid, is the simplest carboxylic
acid with a chemical formula HCOOH. It is a colorless liquid and has a highly
pungent and penetrating odor at ambient. It is also miscible with water and
most polar organic solvent. Methanoic acid is one of the organic raw materials
used in the production of pesticide, leather, dyes, pharmaceuticals and rubber
(Formic Acid Market, 2014). It is applied in animal feed preservation, textiles,
pharmaceuticals, rubber chemicals, and catalysts. It is also in use of the
regulation in pH of chemical processes.
In the industry, methanoic acid is manufactured through the hydrolysis
of methyl formate. Some routes proceed indirectly by first treating the methyl
formate with ammonia to produce formamide, which is then hydrolyzed with
sulfuric acid. The problem with this is the disposal of ammonium sulfate byproduct. With this, an alternative process involving methanoic acid by
hydrothermal oxidation of glucose from a biomass source is believed to be
useful.
Hydrothermal oxidation decomposed sugar content of biomass into
simple carboxylic acid. This conversion into more convenient products getting
more attention because water at high temperature and pressure is an attractive
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solvent and reaction medium exhibits very different properties compared to the
ambient liquid water.
Due to a number of applications of methanoic acid and in order to use
waste like peanut shells, the researchers proposed the study Production of
Methanoic Acid via Hydrothermal Oxidation of Glucose from Peanut
Shells.
STATEMENT OF THE PROBLEM

The Philippines has produced 29,088.93 metric tons of peanut in 2013
(Bureau of Agricultural Statistics). Around 5,817.79 metric tons of peanut
shells are also produced in the Philippines since whole peanuts contain 20%
shell in terms of weight (Hill et. al., 2009).
Incineration was previously done for past years to dispose peanut shells.
But due to environmental concerns, companies find another way to dispose
peanut shells. One of them is the use of peanut shells as feeds for cattle,
poultry, swine, and other farm animals (Wu, 2011).
Aflatoxin contamination in peanut shells is a problem in the Philippines
(Food and Agriculture Organization). Aflatoxin is a carcinogenic mycotoxin
produced by some Aspergillus species. It occurs in sub-tropical and tropical
climates such as the Philippines. High temperature and humidity before and
after harvesting are the major contributing factors in the development of
aflatoxin in cereals and edible nuts, including peanuts (Bureau of Agriculture
and Fisheries Standards, 2015).
The Philippines Food and Drug Administration (FDA) issued consumer
warning after laboratory testing on several locally grow and imported
prepackaged peanuts contained higher than acceptable levels of aflatoxin B1
(Philippine Food and Drug Administration Advisory, 2014).
In the industry, the reaction of methanol and carbon monoxide that
results to methyl formate is performed in the liquid phase at elevated pressure.
The hydrolysis of methyl formate produces formic acid. Some routes of this
process proceeds indirectly to the treatment of methyl formate with ammonia
producing formamaide. This formamide is then hydrolyzed with sulfuric acid
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creating a product of ammonium sulfate. In this industrial process, ammonium
sulfate disposal is a problem. Many factors in performing this industrial
process include the noise and smell it produce.
With this, an alternative process which involves producing methanoic
acid by hydrothermal oxidation of glucose from a biomass source is seemingly
necessary.
Also, in an attempt to reduce the number of affected animals by aflatoxin
and to eliminate the production complications in methanoic acid, the
researchers proposed the study entitled Production of Methanoic Acid via
Hydrothermal Oxidation of Glucose from Peanut Shells.
OBJECTIVES
General
The main objective of the study is to produces methanoic acid from
peanut shells through the hydrothermal oxidation process.
Specific
1. To identify the optimum parameters that will produce the highest
conversion of peanut shells to methanoic acid.
Appearance
Properties
Clear, colorless liquid
Odor
Penetrating, pungent
Density
1.2 g/mL
Boiling Point
101 C
Melting Point
8 C
Viscosity
1.7844 mPa s (20C)
Solubility in Water
Miscible
Flash Point
80 C
Index of Refraction (nD)
1.3714 (20C)
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Surface Tension
37.67 dyne/cm (20C)
2. To identify the optimum parameters that will produce the highest

conversion of peanut shells to methanoic acid.
3. To identify the variations like alkali or acid to be used, concentration
of alkali or acid, ratio of the material to the alkali or acid,
temperature, and time.
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SIGNIFICANCE OF THE STUDY

The research would involve different aspects about the different
sectors of the general public. The following are the fields that the study is
expected to be of importance.
To the Peanut Processors
The study, if proven feasible in small large production and in large scale
production would yield importance to several fields or industry. The following
industries are the ones that is expected that will benefit from this study:
To the Methanoic Acid Industry

The study will help the methanoic acid industries in a way that since
peanut shells are cheap, it is considered as waste by-product. Moreover, the
proposed manufacturing process in this study is simpler and more economical
compared to the other processes on producing methanoic acid.
To the Nation
The study will help the government idealize the utilization of waste
biomass like peanut shells for the production of efficient chemical compounds.
Moreover, applying this study in constructing a manufacturing plant for
methanoic acid creates opportunities in the employment. The job opportunities
includes plant and process engineers that will monitor and maintain the
manufacturing process of the plant, laboratory technicians for Quality Control,
and other jobs that can contribute for the success of the plant.
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SCOPE AND LIMITATIONS OF THE STUDY

The study aimed to produce methanoic acid from peanut shells through
hydrothermal oxidation. The research project included experimentation that
served as the basis for coming up with a manufacturing process that will
produce a high quality methanoic acid.
The study was only limited to the laboratory scale experiment. In
determining the suitable parameters, a number of trials were based on the
existing experimental procedures of various related studies. Variations in the
type of alkali/acid to be used, concentration of alkali/acid, and ratio of the
material to the alkali/acid, temperature, and time are done.
The components of raw material such as a-cellulose, lignin,
hemicelluloses, ash and moisture content were tested by the Philippine Fiber
Industry Development Authority (PhilFIDA) located at Visayas Avenue, Diliman,
Quezon City. In the Adamson University Technology Research and Development
Center (AUTRDC) at Concordia College located in Pedro Gil St., Paco, Manila,
intermediate products from the conversions such as a-cellulose were analyzed.
The analysis of properties of the final product is then determined and tested by
the AUTRDC based on its flashpoint and index of refraction. These properties
were then compared to the commercially-available product in the market.
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METHODS OF RESEARCH
Data gathering was important to the study as it supplied needed
information used for the study. Data should come from reliable sources in
order for the research to be valid.
Gathered data included the properties of the raw material,; standard
properties of the desired product and analysis of the experimental procedures
and manufacturing process involved. The methodology consists of two parts
descriptive and experimental method.
Descriptive Method
The researchers went to different government institutions to gather the
most recent information and statistical data available for the raw material
(peanut shells) and the product (methanoic acid).
Department of Trade and Industry (DTI) Sen. Gil J. Puyat

Avenue, Makati City
- Provided the lists of the consuming and competing industries
and their local production

City Planning and Development Office (Zoning Division)
Bacoor City, Cavite
- Provided the vicinity map, zonal clearance, and land title of the
intended plant location

Others
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-
The researcher also made use of the internet for the most recent
studies and information available locally and internationally.
Experimental Method
Laboratory set-up for experimentations was done and various
parameters were considered to come up with the most appropriate operating
conditions and best quality of the product.
Philippine Fiber Industry Development Authority (PhilFIDA)

Visayas Avenue, Diliman, Quezon City
- Provided the testing for a-cellulose, hemicellulose, lignin, ash,
and moisture content of the peanut shells.

Adamson University Laboratory Testing Center 900 San
Marcelino Street, Ermita, Manila
- Provided the Fourier Transform Infrared (FTIR) Spectroscopy
analysis of the methanoic acid

Adamson University Technology Research and Development
Center (AUTRDC) Concordia College, Pedro Gil, Paco, Manila
- Provided the testing for the a-cellulose, glucose, and methanoic
acid
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CONCEPTUAL FRAMEWORK
Data gathering for the experimental process helped in determining the
best parameters, values and assumptions employed. Set of experiments for
parameter variations were considered in fulfilling the said study.
Experimentation was conducted on a laboratory scale and the values
acquired during the actual experimentation were scaled-up in order to be used
in determining the appropriate manufacturing process.
The experimental study is composed of the following procedures: drying,
size reduction, alkali digestion, acid hydrolysis, and hydrothermal oxidation.
Also on this part, the process on how the researchers test the final product was
also included.
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REVIEW OF RELATED LITERATURE

Raw Material
Peanut Shells
Peanut shells is an abundant
and inexpensive biomass in the
Philippines. It is the by-products of
peanut processing plants. Almost 29
thousand metric tons of peanut have
been harvested annually in the
Philippines with an increasing rate of
3.63%
per
year
(Bureau
of
Agricultural Statistics, 2012). Peanut
shell is 20% by weight of the whole
peanut. This implies that 5800
metric tons of peanut shells are
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Figure 2. Peanut Shells
Peanut Shell Composition

Peanut shell contains structural polysaccharides called cellulose.
Cellulose is an important structural component of the primary cell wall of
green plants (Fang et. al., 2014).
According to the analysis made by the Philippine Fiber Industry
Development Authority, peanut shells has the following chemical composition:
Table 3. Component of Peanut Shell
Component
Percentage (%)
39.86
a-cellulose
47.78
Lignin
10.33
Moisture
2.03
Others
Source: Philippine Fiber Industry Development Authority (FIDA), 2015
a-Cellulose serves as an important component to produce many indemand products nowadays like methanoic acid. With the high proportion of
cellulose in peanut shells, it makes the peanut shell a potentially attractive
partial substitute for making methanoic acid which is widely used by many
industries.
Possible Sources of Peanut Shells

The following are some of the local peanut processors in the Philippines
that utilizes peanut in their production and treat peanut shells as their byproducts.
Table 4. Local Peanut Processors
Company Name
Product
Address
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JBC Food Corporation
Products, Inc.
Dingdong mixed nuts,

Happy nuts, Chikito
cracker nuts, Barnuts,
Milkee Polvoron
Chocomani Candy,
Peanut Spread,
Heavens Choice
Polvoron
Processed peanuts,
Imported Peanuts,
Cashews, Pistachios,
Peanut Butter
Peanut Butter, Crunchy
Peanut Butter
Rodzon Marketing
Peanut Butter
Candy Line Food

Manufacturing
Tobi Marketing Inc.
Newborn Food
Corporation
California
Manufacturing Co. Inc.
Peanut Butter
584 Barrio Llano, Llano

Road, Caloocan, 1400
Metro Manila
Palanas street, Anabu 1,
Imus, Cavite, 4103
Cavite
8526 Juanita De Leon
Street Tobi Marketing
Compoundsucat San
Dionisio, Metro Manila
No. 865, Sto. Cristo
Street, Binondo, Manila,
1006 Metro Manila
2451 Lakandula Street,
Barangay 65, Pasay
City, Metro Manila
Km. 18 East Service
Road, South
Superhighway, Paraaque
City, Paraaque, Metro
Manila
Product
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Methanoic Acid
Methanoic acid, also
known as formic acid, is the
simplest
member
of
the
carboxylic acid family and has
the
molecular
formula
HCOOH. In the carboxyl group
(COOH), the carbon atom has
a double bond joining it to the
oxygen atom and a single
bond joining it to the hydroxyl
Figure 1. Methanoic acid and its structure
Properties
Methanoic acid can be
made
synthethically
in
laboratories. It is colorless and
exists in liquid form. Its freezing point and boiling point is 8.3C and 101C,
respectively. It has a strong, penetrating odor and has a pungent smell. It is
also miscible with water and most polar organic solvents, and is somewhat
soluble in hydrocarbons.
Methanoic acid shares most of the chemical properties of other
carboxylic acids, although under normal conditions, it will not form either an
acyl chloride or an acid anhydride. Until very recently, all attempts to form
either of these derivatives have resulted in carbon monoxide and water. Heat
can also cause methanoic acid to decompose to carbon monoxide and water.
Methanoic acids has the ability to participate in addition reactions with
alkenes. Methanoic acid and alkenes react to form esters. In the presence of
certain acids, like sulfuric and hydrofluoric acids, however, a variant of Koch
reaction takes place instead, and methanoic acid add to alkene producing a
larger carboxylic acid.
The properties of methanoic acid existing in the market is shown below.
Table 2. Properties of Methanoic Acid
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Properties
Appearance
Odor
1.2 g/mL
Density
101C
Boiling Point
8C
Melting Point
1.7844 mPa s (20C)
Viscosity
Miscible
Solubility in Water
80C
Flash Point
1.3714 (20C)
Index of Refraction
37.67 dyne/cm (20C)
Surface Tension
Source: Mallinckrodt Chemicals MSDS, 2005
Applications
Methanoic acid is one of the basic organic chemical raw materials widely
used in pesticide, leather, dyes, pharmaceuticals and rubber industries (Formic
Acid Market, 2014). Major applications include silage and animal feed
preservation,
leather
and
tanning,
textiles,
formate
salts,
pharmaceuticals/food/chemicals, rubber chemicals, catalysts and plasticizers.
In many instances, methanoic acid is used to regulate the pH of chemical
processes.
In animal nutrition, it preserves feed and silage. It is also used as a
pesticide to treat and control mites that infest honey bee hives. In oil field
application, it helps to dissolve calcium carbonate. The pharmaceutical
industry uses methanoic acid as an active ingredient in over-the-counter drug
products. It is also used to create artificial flavors for food and drinks and
artificial scents for perfumes (BASF, 2014)
Recently, it gets more and more attraction to be used as environmental
benign storage and transportation medium for hydrogen. Some researchers
also have demonstrated that methanoic acid has the potential to direct power
fuel cells for the generation of electricity and automobiles (Yun et. Cal., 2010).
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Process
Pretreatment of Raw Material
Pretreatment methods aim the increase in the accessible surface area
and size of pores, and decrease the crystallinity and degrees of polymerization
of cellulose (Taherzadeh et. Al., 2008).
Milling of the dried lignocellulosic biomass aims the size of the size
reduction of the biomass. With milling, only physical size reduction and
increase in the surface area of the biomass is obtained and the lignin of
hemicellulose are not removed (Tatli et. Al., 2013).
Alkali Digestion
Alkali digestion, whereas alkali solutions such as NaOH, Ca(OH) 2or
ammonia are used in lower temperatures and pressures. This process main
action is lignin removal and the removal of acetyl and uronic acid substitutions
on hemicellulose, and breaking ester bonds between lignin and other
components resulting in structural alteration of lignin, cellulose swelling,
partial decrystallization of cellulose and partial solvation of hemicellulose
(Taharzadeh et. Cal., 2008). Alkali digestion is basically a delignification
process, where a significant amount of hemicellulose is also solubilized (Tatli
et. Al., 2013).
Peanut shells + NaOH
a-cellulose + black liquor
Acid
Hydrolysis
Sulfuric acid pretreatment is a principal method in acid hydrolysis of
lignocellulosic biomass. Acid hydrolysis method employs either high acid
concentrations with low temperature or dilute acid concentrations with high
15 | P a g e

temperature (Taherzadeh et. al., 2008). Aside from sulfuric acid, hydrochloric
acid, nitric acid, and phosphoric acid have been studied in biomass
pretreatment (Agbor et. al., 2011). In acid hydrolysis, the cellulose from the
biomass is converted to glucose with the help of a catalyst, which is the
sulfuric acid (Tatli et. al., 2013).
C6H10O5 (cellulose) + H2O H2SO4
C6H12O6 (glucose)
Hydrothermal Oxidation
Hydrothermal oxidation decomposes the sugar content of biomass into
simple carboxylic acid. Non-toxic by-products are produced in this process.
Methanoic acid is a basic product in the hydrothermal oxidation of glucose,
and that 1 mole of glucose can produce 6 moles methanoic acid through the
C6H12O6 (glucose) + 6H2O2 (hydrogen peroxide)
6HCOOH + H2O
addition of hydrogen peroxide (Yun et.al., 2010).
REVIEW OF RELATED STUDIES

Preparation and Conditioning of Peanut Shells
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According to a study by Mosier, 2009, Pretreatment is used on the
cellulose of the biomass since it alters the structure of the cellulose, making it
more accessible.
Proper moisture content of the peanut shells should be observed in the
study since it promotes lower yield if incorrect moisture is applied before
moving on to the next process of the study. Gil (2006) and Wright (2010) stated
that the target moisture in preparing the cellulose is 3% in wet basis.
In the book Biotechnology for Fuels and Chemicals: The Twenty-Eight
Symposium by Mielenz, 2009, it stated that the optimum drying temperatures
lies between 80 C to 120 C, exceeding the values results in yielding burnt
peanut shells. Moreover, in the study of McCoy (2014) Improving Energy
Efficiency through Biomass Drying noted that drying peanut shells for a short
period of time will result in partly dried shells while having it dried for a long
period of time may result in burnt peanut shells, also, the ideal time for drying
the peanut shells is 10 to 30 minutes.
The reduction of crystallinity and increase in overall surface area greatly
increases the total reaction yield according to Hendriks and Zeeman (2009).
Kubata (1994) in his study Agricultural Waste Peanut Shells: A Raw Material for
the Production of Xylose and Xylooligosaccharides, stated that the size of the
peanut shells must be reduced to achieve particles of between 0.1mm to
1.00mm.
Alkali Digestion
Alkali digestion is the process of breaking down the lignin structure and
disrupting the crystalline structure of a-cellulose, so that acids can easily
access and hydrolyze the a-cellulose (Kumar 2009). According also to Kumar in
his study Methods for Pretreatment of Lignocellulosic Biomass for Efficient
Hydrolysis and Biofuel Production in 2009 that sodium, potassium and calcium
hydroxides are suitable for alkaline pretreatment agents.
Furthermore, Felix in his study Comparative Effect of Alkali Treatment on
Chemical Composition and In Vitro Dry Matter and Organic Matter Digestibility of
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Peanut Shells, Soybean Straw and Wheat Straw stated that the concentration of
the alkali solution used for digestion process are ranging from 2% to 6% for
effective exposing and for the conversion to a-cellulose.
In another study by Kubata, Agricultural Waste Peanut Shells, a Raw
Material for the Production of Xylose and Xylooligosaccharides in 1994, it stated
that the approximate ratio of peanut shells to the alkali solution was 1:8.
Furthermore, Kataria, Saccharification of Alkali Treated Biomass of Kans Grass
Contributes High Sugar in Contrast to Acid Treated Biomass in his study in 2013
noted that the temperatures 100 C, 110 C, and 120 C were used for the alkali
treatment. In addition to this, he used different times such as 30, 60, 90 and
120 minutes for the duration of the treatment.
Acid Hydrolysis
Kumar in his study in 2009 (Methods of Pretreatment of Lignocellulosic
Biomass for Efficient Hydrolysis and Biofuel Production) stated that the most
widely used and tested approaches are based in dilute sulfuric acid, in addition
to this, nitric acid and phosphoric acid can also be used. It should be also in
4% wt., since it is inexpensive and effective.
Akpan, The Production of Ethanol from Maize Cobs and Groundnut Shells
in 2005 used 40, 50, 60, 70 and 80C as temperature variants in his study for
hydrolysis of groundnut shells. In addition to this, Martin (Dilute Sulfuric Acid
Pretreatment of Agricultural and Agro-industrial Residues for Ethanol Production)
in 2007 in his study used 20, 40 and 60 mins for the duration of dilute acid
hydrolysis for peanut shells.
Hydrothermal Oxidation
Yun (Formic Acid Production from Carbohydrates Biomass by
Hydrothermal Reaction) in 2010 in his study about hydrothermal reaction
stated that methanoic acid is a basic product in the hydrothermal oxidation of
glucose. He also investigated on the formation of methanoic acid by
hydrothermal oxidation of biomass materials.
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In the study of Akiya (Formic Acid Production from Hydrothermal
Oxidation of Carbohydrates) in hydrothermal oxidation of carbohydrates in
2002, temperatures of 200 C to 350 C were used. Moreover, Jin (Hydrothermal
Oxidation of Carbohydrate Biomass for Producing Hydrogen) in 2008 noted that
the reaction in the conversion of glucose to methanoic acid takes place in about
30 seconds to 90 seconds.
PROCEDURE
A. PREPARATION OF RAW MATERIALS
I.
Raw Material
The main raw material, peanut shells, is collected from JBC Food
Corporation located at Caloocan, Metro Manila with a composition summarized
below.
Table 5. Component of Peanut Shell
Component
Percentage (%)
39.86
a-cellulose
47.78
Lignin
10.33
Moisture
2.03
Others
Source: FTUD REPORT No. 044-14, Philippine Fiber Industry Development
Authority (2015)
The essential component needed from the peanut shells is its a-cellulose
content. This component was then further processes in order to obtain the final
product methanoic acid.
II.
Reagent
Table 2 presents the reagents that were used for the experimental
method. They were purchased from local chemical suppliers such as
Chemodities and Patagonian, both of which are located at Bambang,
Manila; and were used without further purification.
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Table 6. Reagents Used in the Experimental Methodology
Reagent
Chemical
Formula
Molecular
Grade
Boiling
Density
Point
(g/cm3)
40.00
1388.0
2.13
98.09
337.0
1.82
34.02
150.2
1.45
Formula
(g/mol)
Sodium Hydroxide
Chemically
NaOH
Pure
(94% w/w)
Sulfuric Acid
Chemically
H2SO4
Pure
(94% w/w)
Hydrogen Peroxide
Technical
H2O2
Grade
(50% w/w)
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B. DRYING OF PEANUT SHELLS

Drying the peanut shells are important process in this experiment so
that it have the correct moisture content before it proceeds to the next process
for the purpose of maintaining control over the necessary quality. The target
moisture content of the peanut shells is between 3-5% on wet basis (Gil et. Al.,
2006). The researchers are agreed to have a target moisture content of 3%.
Under-drying of peanut shells leads to reduction of percent yield or degrading
the quality of the acid. Over-drying it leads to energy losses.
1. Determination of Drying Temperature
The optimum temperature lies between 80 degrees Celsius to 120 degrees
Celsius (Mielenz et al., Biotechonology for Fuels and Chemicals: The TwentyEighth Symposium, 2009). Above is the process flow chart of determining the
optimum temperature for drying the peanut shells.
1.1 Materials and Apparatus
Peanut Shells
Oven
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Analytical Balance
Stopwatch
1.2 Procedure
1. Weigh five sets of 100 g of peanut shells.
2. Place the first set evenly over the oven tray.
3. Set the temperature of the oven for five trials: 80, 90, 100,110, and
120 degrees Celsius.
4. Dry the peanut shells for 10 minutes.
5. After drying, weigh the dried peanut shells.
1.3 Data and Results
Tria
l
Mass
of
Peanu
t
Shells
(g)
Initial
Moistur
e
Conten
t (%)
Tim
e
(min
)
Temperatu
re (C)
Mass
of
Dried
Peanu
t
Shells
(g)
Moistur
e
Conten
t Loss
(%)
Final
Moistur
e
Conten
t (%)
100
10.33
10
80
95.50
4.50
5.83
100
10.33
10
90
94.78
5.22
5.11
100
10.33
10
100
94.26
5.74
4.59
100
10.33
10
110
93.23
6.77
3.56
100
10.33
10
120
92.54
7.46
2.87
Observation
The peanut
shells are
still wet
The peanut
shells are
still wet
The peanut
shells are
still damp
The peanut
shells are
substantial
ly dry
The peanut
shells are
slightly
burnt
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The optimum temperature based on the experiment is 110C which

significantly removed 6.77% of the moisture content. The moisture content loss
is calculated using the formula:
moisture content loss=
mass before dryingmass after drying

x 100
mass before drying
100 g93.23 g
x 100=6.77
100 g
The initial moisture content of peanut shells in wet basis is 10.33%

(FTUD REPORT No. 044-14, Philippine Fiber Industry Development Authority,
2015). The total moisture content of the dried peanut shells is then calculated
using the formula:
final moisture content=initial moisture contentmoisture content loss
final moisture content=10.33 6.77 =3.56
Since the final moisture content of the dried peanut shells is calculated
to be 3.56%, the 3% target moisture content of the peanut shells was achieved.
2. Determination of Drying Time
However, the drying time for peanut shells is from 10 to 30 minutes
(McCoy Improving Energy Efficiency through Biomass Drying, 2014). Therefore,
experiment was made to determine the optimum time for drying the peanut
shells.
Peanut Shells
Analytical Balance
Oven
Stopwatch
2.2 Procedure
1. Weigh five sets of 100 g of peanut shells.
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2. Place the first set evenly over the oven tray.
3. Set the temperature of the oven to 110 degrees Celsius.
4. Dry the peanut shells for 10, 15, 20, 25 and 30 minutes.
5. After drying, weigh the dried peanut shells.
Tria
l
Mass
of
Peanu
t
Shells
(g)
Initial
Moistur
e
Conten
t (%)
Tim
e
(min
)
Temperatu
re (C)
Mass
of
Dried
Peanu
t
Shells
(g)
Moistur
e
Conten
t Loss
(%)
Final
Moistur
e
Conten
t (%)
100
10.33
10
110
94.16
5.84
4.49
100
10.33
15
110
93.98
6.02
4.31
100
10.33
20
110
92.85
7.15
3.18
100
10.33
25
110
91.78
8.22
2.11
100
10.33
30
110
91.72
8.28
2.05
Observation
The peanut
shells are
still wet
The peanut
shells are
still damp
The peanut
shells are
substantial
ly dry
The peanut
shells
turned
brown
The peanut
shells got
burned
Based from the results, drying at 20 minutes, the final moisture content
and the moisture content loss can be calculated as,
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100 g92.85 g
x 100=7.15
100 g
final moisture content=10.33 7.15 =3.18
Further increasing the time of drying yields moisture content that falls
below the target moisture content for drying. Drying at 30 minutes resulted to
the smallest amount of weight after drying but the peanut shells got burned so
it was not considered as the optimum time for drying.
Therefore, the selected optimum time for drying of peanut shells was 20
minutes.
Equivalent Unit Operation
Unit Operation
Drying
Lab Scale
Oven
Plant Scale
Rotary Dryer
25 | P a g e

C. SIZE REDUCTION
After drying the peanut shells, the next process is size reduction. It is
necessary to reduce the size of it to increase the rate of reaction for the next
process.
1. Determination of the Grinding Time of Peanut Shells
The researchers vary the time of grinding of the peanut shells that will
yield the desired particle size of the peanut shells.
Dried Peanut Shells
Sieve Trays
Blender
Stopwatch
1.2 Procedure
1. From the drying process, use five sets of 90 g of dried peanut shells.
2. Place the first set inside the blender
3. Grind the dried peanut shells for 4, 8, 12, 16, and 20 minutes.
4. Weigh the ground peanut shells
5. Repeat procedure for the remaining four sets.
Trial
Mass of
Dried
Time
(min)
Mass of
Ground
Accumulatio
n (%)
Observatio
n
26 | P a g e

Peanut
Shells (g)
Peanut
Shells (g)
90
88.39
1.79
90
88.61
1.54
Most of the
peanut
shells are
still whole
Some
peanut
shells are
not yet
grinded
All of the
peanut
90
12
88.50
1.67
shells have
been
90
16
88.65
1.50
90
20
88.45
1.72
grinded
Some of the
peanut
shells have
started to
escape as
dust from
the blender
Most of the
ground
peanut
shells
escaped as
dust from
the blender
After the experiment, the optimum time used in grinding peanut shells
will be at 12 minutes. It gives a yield of 1.67% accumulation that is all of the
peanut shells have been grinded. It is computed by,
27 | P a g e

accumulation=
dried peanut s h ellsground peanut s h ells

x 100
dried peanut s h ells
accumulation=
90 g88.50 g
x 100=1.67
90 g
2. Determination of the Particle Size of the Ground Peanut Shells

The particle size of peanut shells were reduced using a blender to
achieve a size between 0.1 and 1.0 mm or 18 and 120 US standard mesh
(Kubata et al., Agricultural Waste Peanut Shells: A Raw Material for the
Production of Xylose and Xylooligosaccharides, 1994)
2.1 Material and Apparatus
Dried Peanut Shells
Sieve Trays
Blender
Stopwatch
Analytical Balance
The researchers vary the particle size of grinding of the peanut shells
that will be used in the next process.
2.2 Procedure
1. From the drying process, use five sets of 85 g of dried peanut shells.
2. Place the first set inside the blender
3. Grind the dried peanut shells for 12 minutes.
4. Record the weight of each pan before and after the screening process.
5. Subtract the weight of the pans after the process and weight of the
pan before the process for the determination fo the weight of the retained
peanut shells.
6. Weigh the ground peanut shells
28 | P a g e

7. Repeat procedure for the remaining four sets.
Mesh
Particle
Size (US
Size
Standard
(mm)
)
Initial Mass
40
0.425
60
0.250
80
0.180
Pan
-
Trial 1
Fraction (g)
Trial 2 Trial 3 Trial 4
Trial 5
Average
Retained
(%)
85
12.37
71.29
1.01
0.33
85
11.99
66.68
5.86
0.47
85
10.75
57.66
16.28
0.31
13.57
73.97
12.04
0.42
85
11.66
60.30
12.81
0.23
85
10.89
58.43
15.21
0.47
The data and results show that the majority of the particles size of the
ground peanut shells is at 60 mesh and below the cumulative percent is under
86.4 percent thus, the remaining 13.57% will be considered as contaminants
in order to prevent non-uniform size quality of ground peanut shells.
Unit Operation
Size Reduction
Lab Scale
Blender, Sieve Trays
Plant Scale
Grinder
D. ALKALI DIGESTION OF GROUND PEANUT SHELLS

Alkali digestion is the process of breaking down the lignin structure and
disrupting the crystalline structure of a-Cellulose, so that the acids can easily
access and hydrolyze the a-Cellulose (Kumar et al., 2009)
Peanut shells + NaOH
a-Cellulose + Black Liquor
1. Determination of the Type of Alkali to be Used
29 | P a g e

Sodium, potassium and calcium hydroxides are the most suitable
alkaline pretreatment agents (Kumar et al., Methods of Pre-treatment of
Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production, 2009).
1.1 Material and Apparatus
Ground Peanut Shells
Analytical Balance
NaOH Solution
Thermometer
KOH Solution
Beaker
Ca(OH)2 Solution
Stirring Rod
Hot Plate
Stopwatch
1.2. Procedure
The procedures for this experiment are the following:
1. Prepare 280 g of 2% (wt/wt) NaOH solution, Ca(OH)2 solution and KOH
solution in three separate beakers.
2. From the grinding process use 70 g of ground peanut shells and place it
3.
4.
5.
6.
in each beaker.
Stir the solution continuously while on the hot plate.
Digest for 30 minutes at 80 degrees Celsius.
Filter the solution.
Dry the residue for an hour at 65 degrees Celsius (Fang et. Al.,
Pretreatment of Peanut Shells, 2014)

7. Record the weight of the dried residue.
8. Compare the mass of the dried residue to the maximum theoretical
amount of a-cellulose then compute for the mass difference.
Mass Difference=Mass of Dried ResidueT h eoretical Mass of acellulose
If
the
mass
difference
is
greater
than
zero,
unnecessary
components of the peanut shells are still attached to the a-cellulose.

If the mass difference is less than or equal to zero, all the
unnecessary components of the peanut shells are removed and the acellulose is therefore completely extracted.
1. 3 Data and Results
30 | P a g e

Mass of
Trial
1
2
3
Ground
Peanut
Shells (g)
70
70
70
Type of
Mass of
Alkali
Residue
Solution
(g)
NaOH
KOH
Ca(OH)2
62.23
63.41
67.35
Mass of
Theoretical
Dried
Mass of a-
Residue
cellulose
(g)
48.24
49.93
53.45
(g)
27.90
27.90
27.90
Mass
Differenc
e (g)
20.34
22.03
25.55
NaOH solution was found to be the most appropriate alkali solution to

be used in alkali digestion since it resulted to a dried residue of 48.24 g with a
mass difference lesser than the two alkali solution. This can be attributed to
the dissociation constants of the three alkali solutions which are given as Na =
0.2; K = 0.5; and Ca = 2.43. These values imply that the lower the pKb value,
the stronger the base.
Since the NaOH solution has the least pKb value, which makes it the
strongest base among the three alkali solutions, it digested the greatest amount
of ground peanut shells.
2. Determination of NaOH Concentration

However, the determination of NaOH Solution has been test. The
applicable concentration is ranging from 2% to 6% for effective exposing and for
the conversion to a-cellulose (Felix et al., Comparative Effect of Alkali Treatment
on Chemical Composition and in Vitro Dry Matter and Organic Matter Digestibility
of Peanut shells, Soybean Straw and Wheat Straw, 1993).

Thermometer
NaOH Solution
Hot Plate
Beaker
Stirring Rod
31 | P a g e

Analytical Balance
Stopwatch
2.2 Procedure
The following procedures are made by the researchers to determine the
optimum concentration of NaOH
1. Prepare 280 g of 2, 3, 4, 5, 6% (wt/wt) NaOH solution in five separate
beakers.
3.
4.
5.
6.
in each beaker.

If
the
mass
difference
is
greater
than
zero,
unnecessary

Trial
1
2
3
Mass of
Ground
Peanut
Shells
(g)
70
70
70
NaOH
Concentration
(wt %)
Mass of
Residue
(g)
Mass of
Dried
Residue
(g)
Theoretical
Mass of acellulose
(g)
Mass
Difference
(g)
2
3
4
62.16
60.94
55.84
48.56
46.88
44.67
27.90
27.90
27.90
20.66
18.98
16.77
32 | P a g e

4
5
70
70
5
6
55.49
53.93
43.35
43.14
27.90
27.90
15.45
15.24
A solution of 5% NaOH was found to be the most appropriate

concentration for alkali digestion with a mass difference of 15.45 g. further
increasing the NaOH concentration to 6% had a minimal change in the mass
difference (15.24 g) with respect to the maximum theoretical amount of acellulose that can be obtained.
3. Determination of Ratio of Ground Peanut Shells to NaOH Solution

After determining the most applicable solution and its concentration, the
next step is to determine the most appropriate ratio of ground peanut shells to
NaOH Solution. The ratio of peanut shells to NaOH solution used in alkali
digestion is 1 is to 8. (Agricultural Waste Peanut Shells, a Raw Material for the
Production of Xylose and Xylooligosaccharide, Kubata et al., 1994).
Thermometer
NaOH Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
The values near this ratio will be examined to determine the most
applicable ratio for this experiment.
3.2 Procedure
The following procedures are done to determine the most applicable ratio.
1. Prepare 280, 420, 560, 700, and 840 g of 5% (wt/wt) NaOH solution in
five separate beakers.
in each beaker.
33 | P a g e

3.
4.
5.
6.


If
the
mass
difference
is
greater
than
zero,
unnecessary

Ratio of
Mass of Ground
Mass of
Mass of Theoretical
Ground Peanut
Mass of
Mass
NaOH
Dried
Mass of aTrial Peanut
Shells
Residue
Difference
Solution
Residue
cellulose
Shells
to
(g)
(g)
(g)
(g)
(g)
(g)
NaOH
Solution
1
70
1:4
280
56.21
43.57
27.90
15.67
2
70
1:6
420
53.87
41.44
27.90
13.54
3
70
1:8
560
49.86
39.26
27.90
11.36
4
70
1:10
700
48.76
38.09
27.90
10.19
5
70
1:12
840
47.77
37.91
27.90
10.01
A ratio of 1:10 (ground peanut shells: NaOH solution) was found to be
the most appropriate ratio for alkali digestion with a mass difference of 10.19
g. Further increasing the temperature to 1:12 had a minimal change in the
34 | P a g e

mass difference (10.01 g) with respect to the maximum theoretical amount of
a-cellulose that can be obtained.
4. Determination of Alkali Digestion Temperature

The next process is to determine the most appropriate temperature for
alkali digestion. In a study by Kataria et al., (2013) on Saccharification of Alkali
Treated Biomass of Kans Grass Contributes Higher Sugar in Contras to Acid
Treated Biomass, the temperatures 100, 110, and 120 degrees Celsius were
used for the NaOH pretreatment. Variations such as 80 and 90 degrees Celsius
were added to employ five trials in the process.
Thermometer
NaOH Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
4.2 Procedure
The following procedures are done by the researchers.
1. Prepare 700 g of 5% (w/w) NaOH solution in five separate beakers.
3.
4.
5.
6.
in each beaker.
Digest for 30 minutes at 80, 90, 100, 110, and 120 degrees Celsius.

35 | P a g e

If
the
mass
difference
is
greater
than
zero,
unnecessary

Mass of
Ground
Temperature
Trial
Peanut
(C)
Shells
(g)
1
70
80
2
70
90
3
70
100
4
70
110
5
70
120
A temperature of 100C
temperature for alkali digestion
Mass of
Residue
(g)
Mass of
Dried
Residue
(g)
Theoretical
Mass of acellulose
(g)
Mass
Difference
(g)
49.45
38.33
27.90
10.43
46.88
36.06
27.90
8.16
43.89
34.02
27.90
6.12
42.61
33.81
27.90
5.91
42.09
33.67
27.90
5.77
was found to be the most appropriate
with a mass difference of 6.12 g. further
increasing the temperature to 110 and 120C had a minimal change in the
mass difference (5.91 and 5.77 g, respectively) with respect to the maximum
theoretical amount of a-cellulose that can be obtained.
5. Determination of Alkali Digestion Time

In a study made by Kataria et al., (2013) on Saccharification of Alkali
Treated Biomass of Kans Grass Contributes Higher Sugar in Contras to Acid
Treated Biomass used different times such as 30, 60, 90, and 120 minutes for
the NaOH pretreatment.
Thermometer
36 | P a g e

NaOH Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
5.2 Procedure
The following procedures are done by the researchers.
1. Prepare 700 g of 5% (w/w) NaOH solution in five separate beakers.
3.
4.
5.
6.
in each beaker.
Digest for 30, 60, 90, and 120 minutes at 100 degrees Celsius.

If
the
mass
difference
is
greater
than
zero,
unnecessary

Trial
1
2
Mass of
Ground
Peanut
Shells (g)
70
70
Time
(min)
Mass of
Residue
(g)
30
60
43.68
38.54
Mass of
Dried
Residue
(g)
33.86
30.11
Theoretical
Mass of acellulose
(g)
27.90
27.90
Mass
Difference
(g)
5.96
2.21
37 | P a g e

3
4
70
90
37.86
29.81
27.90
1.91
70
120
37.06
29.65
27.90
1.75
A time of 60 minutes was found to be the most appropriate time for
alkali digestion with a mass difference of 2.21 g. further increasing the time to
90 and 120 minutes had a minimal change in the mass difference (1.91 and
1.75 g, respectively) with respect to the maximum theoretical amount of acellulose that can be obtained.
Based on the laboratory testing dine by the Adamson University
Technology Research and Development Center on the extracted product after
the alkali digestion process , a-cellulose content of 26.60% was obtained from
the 39.86% a-cellulose component of the peanut shells. Thus, the efficiency of
the process can be calculated as percentage yield by
yield=
experimental acellulose obtained

26.60
x 100=
x 100=66.73
original acellulose present
39.86

Unit Operation
Alkali Digestion
Lab Scale
Hot Plate, Beaker
Plant Scale
Digester
E. ACID HYDROLYSIS OF A- CELLULOSE

Acid hydrolysis effectively removes and recovers most of the
hemicelluloses as dissolved sugars, and glucose yields from cellulose increase
with hemicelluloses removal to almost 100% for complete hydrolysis.
38 | P a g e

Hemicelluloses are removed when acid is added and this enhances digestibility
of cellulose in the residual solids. (Kumar et al., 2009).
From the alkali digestion process, 30 g of a-cellulose will be used for acid
hydrolysis. The maximum theoretical amount of glucose that can be obtained
from the conversion of a-cellulose based on the chemical reaction can be
calculated as
30 g acellulose x
1mol
1 mol glucose
180.18 g
x
x
=33.33 g glucose
162.16 g 1 mol acellulose
1 mol
This value will be used in the determination of the best parameters for
acid hydrolysis.
1. Determination of the Type of Acid Solution to be Used

For the determination of the type of acid solution to be used, the
researchers variations are based on the study of Kumar et al., Pretreatment of
Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production, 2009.
According to her study, the most widely used and tested approaches are based
on dilute sulfuric acid. However, nitric acid and phosphoric acid have also been
tested.
a-cellulose
Thermometer
Acid Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
1.2 Procedure
The following procedures are made by the researchers.
39 | P a g e

1. Prepare 30 g of 1% (w/w) H2SO4 solution, HNO3 solution and H3PO4
2.
3.
4.
5.
solution in three separate beakers.

From the alkali digestion process, use 30 g of a-cellulose in each beaker.
Hydrolyze for 20 minutes at 50 degrees Celsius.
Record the weight of the glucose produced.
Trial
1
2
3
Mass of acellulose (g)

30
30
30
Type of Acid
Solution
H2SO4
HNO3
H3PO4
Mass of
Glucose (g)
23.52
20.25
15.01
Conversion
(%)
70.57
60.76
45.03
After the experiment, the percent conversion for every acid was
determined using the following formula:
conversion=
mass of glucose produced

x 100
maximum t h eoretical amount of glucose
conversion=
23.52 g
x 100=70.57
33.33 g
The sulfuric acid solution was found to be the most appropriate acid
solution to be used in acid hydrolysis. Since the sulfuric acid solution has
the least pKa value, which makes it the strongest acid among the three acid
solutions, it hydrolyzes the greatest amount of a-cellulose.
3. Determination of the Ratio of a-Cellulose to H2SO4 Solution

However, the determination of the ratio of a-cellulose to H2SO4 solution
will be having a variations of 1:1, 1:2, and 1:3. (Production of Ethanol from
Maize Cobs and Groundnut Shells, Akpan et al., 2005).
40 | P a g e

a-cellulose
Thermometer
Acid Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
3.2 Procedure
The following procedures are made by the researchers.
1. Prepare 30, 60, and 90 g of 2% (w/w) H2SO4 solution in three separate
2.
3.
4.
5.
beakers.
Hydrolyze for 20 minutes at 50 degrees Celsius.
Trial
1
2
3
30
30
30
Ratio of a-
Mass of
cellulose
H2SO4
to H2SO4
Solution
1:1
1:2
1:3
Solution
Mass of
Glucose (g)
Conversion
(%)
(g)
30
60
90
24.52
25.06
25.19
73.57
75.19
75.58
After the experiment, the percent conversion for every acid was
determined using the following formula:
conversion=

x 100
conversion=
25.06 g
x 100=75.19
33.33 g
41 | P a g e

And hence, the best ratio of a-cellulose to sulfuric acid solution for the
acid hydrolysis is 1:2 which yielded 75.19% conversion of a-cellulose into
glucose.
4. Determination of Acid Hydrolysis Temperature

For the determination of acid hydrolysis time and temperature, 40, 50,
60, 70, and 80 degrees Celsius are used as variations. (Akpon et al., 2005)
a-cellulose
Thermometer
Acid Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
4.2 Procedure
The following are the procedures to determine the optimum value
for each parameters.
1.
2.
3.
4.
5.
Prepare 60 g of 2% (w/w) H2SO4 solution in three separate beakers.

Hydrolyze for 20 minutes at 50, 60, 70, 80, 90 degrees Celsius.
Trial
1
2
3
4
5

30
30
30
30
30
Temperature
(C)
50
60
70
80
90
Mass of
Glucose (g)
25.11
26.16
26.69
27.37
27.55
Conversion
(%)
75.34
78.49
80.08
82.12
82.66
42 | P a g e

A temperature of 80C was found to be the most appropriate temperature
for acid hydrolysis. At 80C, the conversion of a-cellulose into glucose can
be calculated by:
%conversion= maximumtheoretical amount of glucose 100
27.37 g
%conversion= 33.33 g 100
%conversion=82.12%
Further increasing the temperature to 90C only had a little increment of
conversion (0.54%).
5. Determination of Acid Hydrolysis Time

The variations are 20, 40, and 60 minutes of dilute acid hydrolysis of
peanut shells. (Martin, et al.)

a-cellulose
Thermometer
Acid Solution
Hot Plate
Beaker
Stirring Rod
Analytical Balance
Stopwatch
5.2 Procedure
The following are the procedures to determine the optimum value
for each parameters.
1.
2.
3.
4.
Prepare 60 g of 2% (w/w) H2SO4 solution in three separate beakers.

Hydrolyze for 20, 40, 60, 80 minutes at 80 degrees Celsius.
43 | P a g e

5. Record the weight of the glucose produced.
Mass of aMass of
Conversion
Time (min)
cellulose (g)
Glucose (g)
(%)
1
30
20
27.35
82.06
2
30
40
28.76
86.29
3
30
60
30.12
90.37
4
30
80
30.29
90.88
At a time of 60 minutes was found to be the most appropriate time for
acid hydrolysis. At 60 minutes, the conversion of a-cellulose into glucose
can be calculated by:
Trial
conversion=

x 100
conversion=
30.12 g
x 100=90.37
33.33 g
Further increasing the time to 80 minutes only had a little increment of

conversion (0.51%).
Unit Operation
Acid Hydrolysis
Lab Scale
Hot Plate, Beaker
Plant Scale
Hydrolyzer
F. HYDROTHERMAL OXIDATION OF GLUCOSE

Hydrothermal oxidation is the process of converting glucose into
methanoic acid with the use of an oxidizer. The basic product of hydrothermal
oxidation of glucose is methanoic acid, and that 1 mole of glucose can produce
6 moles of methanoic acid.
C6H12O6 + 6H2O2
6HCOOH + 6H2O
44 | P a g e

Since 1 mole of C6H12O6 will react to form 6mol of HCOOH based on the
chemical reaction, the maximum theoretical amount of methanoic acid that
can be obtained is calculated as
0.1665 mol C 6 H 12O 6 x
6 mol HCOOH
46.03 g HCOOH
x
=45.98 g glucose
1 mol C 6 H 12 O 6 1 molHCOOH
1. Determination of Hydrothermal Oxidation Temperature

The study entitled Formic Acid Production from Hydrothermal Oxidation of
Carbohydrates by Akiya et. al. (2002), experiments were performed at
temperatures from 200 to 350 degrees Celsius. The temperature of 350C was
omitted from the variations employed in this process since it was not attainable
due to lack of necessary equipment.
Glucose
Thermometer
H2O2 Solution
Hot Plate
Improvised Autoclave
Stirring Rod
Analytical Balance
Stopwatch
1.2 Procedure
The procedures for the following parameters are shown below.
1. Prepare 72 g of 30% (w/w) Hydrogen Peroxide solution in five separate
2.
3.
4.
5.
6.
beakers.
From the acid hydrolysis process, use 30 g of glucose in each beaker.
React at 200, 250, and 300 degrees Celsius.
Record the weight of the methanoic acid produced.
Compare the mass of the methanoic acid produced to the maximum
theoretical amount of product that can be obtained then compute for the
mass difference.
45 | P a g e

Mass Difference=Mass of HCOOH producedT h eoretical Mass of HCOOH
If the mass difference is greater than zero, impurities are still

present in the methanoic acid.
impurities are removed from the methanoic acid.
Mass of
Trial
Glucose
(g)
1
2
3
30
30
30
Mass of
H2O2
Temperature
Solutio
(C)
n (g)
72
72
72
200
250
300
Mass of
Methanoic
Acid (g)
75.48
70.25
68.09
Theoretical
Amount of
Methanoic
Acid (g)
45.98
45.98
45.98
Mass
Difference
(g)
29.50
24.27
22.11
A temperature of 250C was found to be the most appropriate

temperature for hydrothermal oxidation with a mass difference of 24.27 g.
Further increasing the temperature to 300C may result to inefficient use of
energy since it only had a minimal change in the mass difference (22.11 g) with
respect to the maximum theoretical amount of methanoic acid that can be
obtained.
2. Determination of Hydrothermal Oxidation Time
A study entitled Methods for Pretreatment of Lignocellulosic Biomass for
Efficient Hydrolysis and Biofuel Production by Kumar et. al. (2009) stated that
sulfuric acid at concentrations usually below 4 wt% has been one of the most
interest in such studies as it is inexpensive and effective.
a-Cellulose
Beaker
Acid Solution
Analytical Balance
46 | P a g e

Thermometer
Stirring Rod
Hot Plate
Stopwatch
47 | P a g e
2.2 Procedure
The procedures for the following parameters are shown below.
1. Prepare 72 g of 30% (w/w) Hydrogen Peroxide solution in five separate
2.
3.
4.
5.
6.
beakers.
From the acid hydrolysis process, use 30 g of glucose in each beaker.
React for 30, 45, 60, 75 and 90 seconds.
Record the weight of the methanoic acid produced.
Compare the mass of the methanoic acid produced to the maximum
theoretical amount of product that can be obtained then compute for the
mass difference.
Mass Difference=Mass of HCOOH producedTheoretical Mass of HCOOH
If the mass difference is greater than zero, impurities are still present in
the methanoic acid.
If the mass difference is less than or equal to zero, all the impurities are
removed from the methanoic acid.
Trial
1
2
3
4
5
Mass of
Glucose
(g)
30
30
30
30
30
Mass of
H2O2
Solution
(g)
72
72
72
72
72
Time (s)
Mass of
Methanoic
Acid (g)
Theoretical
Amount of
Methanoic
Acid (g)
Mass
Difference
(g)
30
45
60
75
90
69.81
56.26
45.72
37.17
28.91
45.98
45.98
45.98
45.98
45.98
23.83
10.28
-0.26
-8.81
-17.07
After testing the parameters, the best time to be used in hydrothermal

oxidation of glucose is 60 seconds with a negative mass difference of -0.26 g;
hence, impurities in the methanoic acid are removed and the glucose had been
converted. Prolonging the time to 75 and 90 s will significantly evaporate the
methanoic acid.
G. TESTING
The methanoic acid is then tested for its properties. The following
properties can be observed after obtaining methanoic acid from the
experimental process:
Table 5. Physical Properties of Methanoic Acid Produced
Properties
Clear Colorless Liquid
Appearance
Odor
The methanoic acid tested using Fourier Transform infrared (FTIR)
Spectroscopy has a peak value of 1700.71 cm -1 which is within the range of the
peak value of commercially available ones(1700-2970cm-1).
However, conformance of the peak value only confirms the presence of

carboxylic acid the sample. Further testing were done to make use that
methanoic acid and no other types of carboxylic acid was produced in the
study. For this, refractive index of methanoic acid was also tested using ABBE
Refractometer in Adamson University Technology Research and Development
Center.
Properties
Standard
Index of Refraction (nD)
1.3714 (20C)
Obtained from this

Study
1.3780
The table shows that the index of refraction of the methanoic acid in this
study is close to the index of refraction of methanoic acid that is commercially
available. Furthermore, it can be made sure that the index of refraction
obtained is for a carboxylic acid specifically methanoic acid since the values for
index of refraction for other carboxylic acids are different.
Carboxylic Acid
Methanoic Acid
Acetic Acid
Lactic Acid
Proprionic Acid
Refractive Index
1.3714
1.4135
1.4270
1.3860
Lastly, the flashpoint of methanoic acid obtained from this study was
tested using Open-Cup Calorimeter in Adamson University Technology
Research and Development Center. The flash point of a volatile material is the
lowest temperature at which it can vaporize to form an ignitable mixture in air.
Measuring a flash point requires an ignition source. At the flash point, the
vapor may cease to burn when the ignition source is removed.
Properties
Standard
Flash Point (C)
80
Obtained from this

Study
80
The above table shows that the flashpoint for the methanoic acid
obtained from this study is the same as the flashpoint of commercially
available ones. Furthermore, table 6 presents the flash point for other types of
carboxylic acid.
Table 6. Flashpoint of Different Types of Carboxylic Acid
Carboxylic Acid
Methanoic Acid
Acetic Acid
Lactic Acid
Proprionic Acid
Flash Point (C)

80
40
110
69
As a summary, the following are the properties of methanoic acid tested

in this study.
Properties
Appearance
Odor
Peak Value
Refractive Index
Flash Point
Value
1700.71 cm-1
1.3780
80C
SUMMARY OF EQUIVALENT UNIT OPERATIONS

(Laboratory Scale to Industrial Scale)
Unit
Laboratory
Industrial
Operation
Scale
Scale
Drying
Oven
Rotary Dryer
Size Reduction
Blender, Sieve
Trays
Grinder
Alkali
Digestion
Hot Plate,
Beaker,
Thermometer,
Stirring Rod
Digester
Filtration
Filter Paper,
Funnel
Plate and
Frame Filter
Press
Purpose
To remove
excess
moisture that
may affect
succeeding
processes
To reduce the
size of the
peanut shells
so as to
increase the
rate of reaction
in the
conversion
processes
To extract the
a-cellulose
content of
peanut shells
through the
removal of
lignin and
hemicellulose
To separate the
a-cellulose
(solid) from the
lignin and
hemicellulose
(liquid)
Acid Hydrolysis
Hydrothermal
Oxidation
Hot Plate,
Beaker,
Thermometer,
Stirring Rod
Autoclave
Hydrolyzer
To convert the
a-cellulose into
glucose
Oxidizer
To produce
methanoic acid
from glucose
SUMMARY OF PARAMETERS
Unit Operations
Drying
Size Reduction
Alkali Digestion
Acid Hydrolysis
Hydrothermal
Oxidation
Parameters
Temperature
Time
Time
Particle size
Type of alkali solution to
be used
Alkali concentration
Ratio of peanut shells to
alkali solution
Temperature
Time
Type of acid solution to
be used
Acid concentration
Ratio of a-cellulose to
acid solution
Temperature
Time
Type of oxidant
Oxidant concentration
Ratio of glucose to
oxidant
Temperature
Time
Values
110C
20 minutes
12 minutes
60 mesh
NaOH
5 wt%
1:10
100C
60 minutes
H2SO4
2 wt%
1:2
80C
60 minutes
H2O2
30 wt%
1:2.4
250C
60 seconds
30 g of glucose was placed in a beaker. the glucose was

reacted with 72 g of 30 wt% H2O2 solution with a ratio
of 1:2.4 (glucose:oxidant) at 250C for 60 seconds.
then, 45.72 g of methanoic acid was produced.
Hydrothermal
Oxidation
Alkali
Digestion
70 g of ground peanut shells was placed in a beaker.

then, 700 g of 5 wt% NaOH solution with a ratio of
1:10 (peanut shells:alkali solution) was employed for
the aklaki digestion. this was carried out at 100C for
60 minutes. the digested product was then filtered.
Acid
Hydrolysis
30 g of a-cellulose was placed in a beaker. this process

was catalyzed byy a 60 g of 2 wt% H2SO4 solution with
a ratio of 1:2 (a-cellulose:acid solution) and the
reaction was operated at 80C for 30 minutes. the acellulose was then converted into glucose.
90 g of dried peanut shells was then size reduced

though a blender for 12 minutes then it was subjected
to a 60 mesh screen.
100 g of peanut shells was placed evenly over the oven

tray. it was dried at 110C for 20 minutes to lower the
moisture content from 10% to 3%.
Size
Reduction
Drying
EXPERIMENTAL PROCESS FLOW DIAGRAM
CONCLUSION
In the conceptual framework, our group did not include the market
study, technical study, and economic study of the document. We focused
on the experimental study of the document. The researchers briefly
discussed what will happen in the experiment. It includes the steps,
scope and limitations of the experiment.
The researchers objectives were attainable. They stated all the
properties needed to be test in order to accomplish the research purpose
and that can help solve the research problem. They include all the
possible information that the research should obtained. It includes the
standard properties of a methanoic acid that will be the basis of
acceptability in the market of the research product (methanoic acid from
peanut shells). The methods of projection of data of the demand and
supply of the product were also included. Also the detailed
manufacturing process for the production and the equipment needed to
be specified. All are leading to the basic information of the research
product
Moreover, in the section of review of related studies, the researchers
gathered enough studies and claims to support their study. It can also be
noted that the researchers did not only followed what was claimed in
other studies but also did their own variation in data, which can be
observed in the data and results of the study.
From the temperatures, ratio of materials and duration of reaction,
the researchers gave their study a solid foundation of studies. However,
this may affect the research to lose its originality since the study is
heavily dependent in the study of Yun, Jin, and Akiya since the process
is based in Hydrothermal Oxidation of biomasses but in overall, The
principles of the studies behind the research is concise and clear, this
gives the research a concrete foundation of principles behind different
processes that is used in the proposed experiment.
In the experimental procedure, our group did notice the
consistency for every procedure. It obeys their review of related literature
and review of related studies. Each step has a basis and steps that are
vague or not clear were properly determined using different variables.
But despite of this properly documented procedure, we have one
question, Is it possible that theyve done all of this procedure correctly
and perfectly? We arrived with this question because it seems they have
no recommendations in relation to it and did not include some errors on
their procedures. But overall, the experimental procedure is well
supported by the review of related literature and studies.
RECOMMENDATIONS
For the further improvement of the study, we suggest that:
1. For further efficiency of the final product, the researchers must use more
specific variations which do not rely only on numbers divisible by five
and ten.
2. The venue of the experiment must be fit for environment with standard
temperature and pressure so that in the manufacturing process for mass
production of this product is standardized.
3. The researchers must also indicate on how the final product will be
packaged.
4. As much as possible, the researchers must not rely on one or two review
of related literature and studies. This part must be plenty as much as
possible so that the best variation will be determined for the experiment.
5. The researchers must determine and include the possible errors during
the experiment and make some assumptions on how it will be avoided.

Summary of Experimentation of Hydrothermal Oxidation of Glucose For The Production of Methanoic Acid

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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

Pamantasan ng Lungsod ng Maynila

STATEMENT OF THE PROBLEM

Pamantasan ng Lungsod ng Maynila

1.7844 mPa s (20C)

Index of Refraction (nD)

Pamantasan ng Lungsod ng Maynila

37.67 dyne/cm (20C)

2. To identify the optimum parameters that will produce the highest

Pamantasan ng Lungsod ng Maynila

SIGNIFICANCE OF THE STUDY

To the Methanoic Acid Industry

Pamantasan ng Lungsod ng Maynila

SCOPE AND LIMITATIONS OF THE STUDY

Pamantasan ng Lungsod ng Maynila

Department of Trade and Industry (DTI) Sen. Gil J. Puyat

and their local production

intended plant location

Pamantasan ng Lungsod ng Maynila

Philippine Fiber Industry Development Authority (PhilFIDA)

and moisture content of the peanut shells.

analysis of the methanoic acid

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

REVIEW OF RELATED LITERATURE

Pamantasan ng Lungsod ng Maynila

Peanut Shell Composition

Possible Sources of Peanut Shells

Pamantasan ng Lungsod ng Maynila

Dingdong mixed nuts,

Candy Line Food

Tobi Marketing Inc.

584 Barrio Llano, Llano

Pamantasan ng Lungsod ng Maynila

Figure 1. Methanoic acid and its structure

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

a-cellulose + black liquor

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addition of hydrogen peroxide (Yun et.al., 2010).

REVIEW OF RELATED STUDIES

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Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

B. DRYING OF PEANUT SHELLS

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Pamantasan ng Lungsod ng Maynila

The optimum temperature based on the experiment is 110C which

mass before dryingmass after drying

moisture content loss=

The initial moisture content of peanut shells in wet basis is 10.33%

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

final moisture content=10.33 7.15 =3.18

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

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dried peanut s h ellsground peanut s h ells

2. Determination of the Particle Size of the Ground Peanut Shells

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