Proposal 3

PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila

College of Engineering and Technology
Department of Chemical Engineering
Chemocatalytic Conversion of Crude Glycerol

and Liquefied Coconut Coir Lignocellulose for
the Production of Polyurethane Aerogel
Superinsulator
DIONISIO, Charles Amiel P.

FULUGAN, Ceazar Justine L.
REDUBLO, Anne Paulinne P.
SAYA, Diana Jane S.
June 14, 2017
Chemocatalytic Conversion of Crude Glycerol and Liquefied Coconut Coir Lignocellulose for the
Production of Polyurethane Aerogel Superinsulator 1
TABLE OF CONTENTS
CHAPTER I: Introduction
Background of the Study
Statement of the Problem
Objectives
Significance of the Study
CHAPTER II: Review of Related Literature and Studies

Raw Materials
Process
Product
Testing
CHAPTER I
Introduction
BACKGROUND OF THE STUDY
Crude glycerol is a by-product of the biodiesel which is considered to be a promising

alternative and renewable fuel. According to the Global Agricultural Information Network, the
Philippines produced 350 million liters of biodiesel in 2016 and its crude glycerol generation
is about 30.38 million liters. In connection to this, the Biofuels Act or Republic Act (RA) 9367
that has mandated a minimum one percent biodiesel blend in all diesel fuels on 2007,
which was then raised to 2% by 2009, then 5% by 2015, projected to 10% increased by
2020, and to 20% by 2030 showed that crude glycerol generation will also increase.
Coconut coir is a by-product of the coconut palm processing. According to Philippine

Statistics Authority, the production of coconut in the Philippines amounts to 14,735,200
Metric Tons (MT) which then yield coconut coir. Since the Philippines is world’s second
largest producer of coconut (Calderon, 2013), the utilization of coir will be highly
recommended.
Significant industrial interest exists with respect to the development of innovative

efficient materials for thermal insulation applications. Many research and development
studies have long focused on materials like aerogels because they are lightweight and
boasts a thermal conductivity that is 2 to 3 times lower than that of conventional fiberglass
insulation (Dourbash, 2016).
Most studies deal with inorganic silica aerogels that can be considered as
superinsulating materials, but which have generally poor mechanical properties, and have
very expensive chemical precursors (Rigacci, 2004). Polyurethanes, like other polymers, rely
on petroleum feedstock’s, however biomass, vegetable oils or industrial by-products have
been used to replace petroleum based polyols in the synthesis of polyurethanes with
excellent results (Gama et. al, 2017).
Polyurethane Aerogel Superinsulator is a special type of insulating material that is

made from naturally occurring materials. The unique property of this type of insulator is its
low effective thermal conductivity. This type of insulating material can be derived from
materials such as crude glycerol and coconut coir through the process of chemocatalytic
conversion.
The abundance of the crude glycerol and coconut coir and its potential to produce a
polyurethane aerogel superinsulator, the researchers initiated the study “Chemocatalytic
Conversion of Crude Glycerol and Liquefied Coconut Coir Lignocellulose for the Production of
Polyurethane Aerogel Superinsulator”.
STATEMENT OF THE PROBLEM
Crude glycerol is the main by-product of biodiesel production. In general, for every
100 pounds of biodiesel produced, approximately 10 pounds of crude glycerol are created.
With the demand and production of biodiesel growing exponentially, the utilization of the
crude glycerol becomes an urgent topic.
For large scale biodiesel producers, crude glycerol can be refined into a pure form
and then be used in food, pharmaceutical, or cosmetics industries. For small scale
producers, however, purification is too expensive to be performed in their manufacturing
sites. Their crude glycerol is usually sold to large refineries for upgrading. In recent years,
however, with the rapid expansion of biodiesel industry, the market is flooded with excessive
crude glycerol. As a result, biodiesel producers only receive 2.5-5 cents/lb for this glycerol
(Johnson and Taconi, 2007). It is important to note that the excess of crude glycerol
produced in the biodiesel industry is leading to a decrease in glycerol prices and glycerol is
now considered a waste instead of a coproduct (Yazdani and Gonzales, 2007)
Similarly, coconut production has yielded major wastes like coconut husk.
Approximately 500 million coconut trees in the Philippines produce tremendous amounts of
biomass as husk which is approximately 4.1 million tons. (Zafar, 2015). The coconut husk
has always been thrown to waste by farmers after copra production. Such poor farming
approach contributes to an environmental problems. The husks are thrown to rivers or just
simply piled up in a corner to rot. (Caoyonan, 2013).
With the massive generation of crude glycerol and coconut coir lignocellulose from
coconut husk, and to provide a solution by converting it into a high value added product, the
researchers proposed the study titled “Chemocatalytic Conversion of Crude Glycerol and
Liquefied Coconut Coir Lignocellulose for the Production of Polyurethane Aerogel
Superinsulator”.
OBJECTIVES OF THE STUDY

Main Objective
The main objective of this study was to utilize the Crude Glycol and the Coconut Coir
for the production of Polyurethane Aerogel Superinsulator through the process of
Chemocatalytic Conversion.
Specific Objective
The study also aims to achieve the following objectives:

 To produce a polyurethane aerogel superinsulator derived from crude glycerol and
coconut coir lignocellulose that will conform to the properties of the standard and
existing product shown in table provided
Property Standard Existing Proposed
density [g/cm3] 0.18
Compressive strength [MPa] 7.8
Thermal conductivity [W/m-K] 0.029 0.017
 To devise an experimental method and determine the optimum operating conditions

that would yield a polyurethane aerogel superinsulator with properties adhering to
the standard and existing product
 To determine the market feasibility of polyurethane aerogel superinsulator through
the analysis of the projections of the demand and supply of the product.
 To design a complete manufacturing process, equipment and transport utilities that
will enable the company to produce quality polyurethane aerogel superinsulator
SIGNIFICANCE OF THE STUDY
To the Students & Researchers
This study will serve as an additional reference for students and researchers
who are developing alternative production process in producing an insulating
material such as polyurethane aerogel superinsulator from an abundant industrial by-
product.
To the Chemical Engineering Profession

Since the chemical engineering field’s major role is to convert raw materials
into useful products, the production of polyurethane aerogel superinsulator would
attract professionals to conduct more studies related to the utilization of crude
glycerol and coconut coir and also to the application of supercritical drying on other
aerogel insulation products.
To the Biodiesel Producers

The study provides a new method to utilize the crude glycerol by-product from
the production of biodiesel fuel. Through this, the biodiesel companies would be able
to reduce the excessive crude glycerol generation.
CHAPTER II
Review of Related
Literature and Studies
REVIEW OF RELATED LITERATURE AND STUDIES
Presented in this chapter are the various studies and literature relevant to the
research title “Chemocatalytic Conversion of Crude Glycerol and Liquedfied Coconut Coir
Lignocellulose for the Production of Polyurethane Aerogel Superinsulator”. Information
about the raw material to be utilized, the process to be employed and the product to be
produced are the main focus of this chapter.
Figure 2.1. Crude Glycerin or Crude Glycerol
Crude Glycerol also known as crude glycerin (as shown in Figure 2.1) is a major
byproduct in the biodiesel manufacturing process. Biodiesel, one of the promising
alternative and renewable fuels, has been viewed with increasing interest and its production
capacity has been well developed in recent years. As its production increases, so does
production of the principle co-product, crude glycerol. Because this glycerol is expensive to
purify for use in the food, pharmaceutical, or cosmetics industries, biodiesel producers must
seek alternative methods for its disposal. Various methods for disposal and utilization of this
crude glycerol have been attempted, including combustion, composting, anaerobic
digestion, animal feeds, and thermochemical/biological conversions to value-added

products. (Yang et al., 2012).
In this study, it is important to determine whether the raw material to be used is

abundant enough to be continually used for the production. According to Philippine
Department of Energy (DOE), there were 11 registered and operational biodiesel refineries
in 2014, with an aggregate annual capacity of 585 Million Liters (MLi). In 2012, the same
number of refineries was registered but only nine (9) were operational. Total capacity
increased 48 percent from 393 MLi in 2013 to 585 MLi in 2014. Additionally, the average
annual production of biodiesel was 172 Million Liters (MLi) in 2014 and was increased to
190 MLi on 2015. Based on DOE data, except for 2010, biodiesel production has been
increasing since the implementation of the Biofuels Act and was expected to continue to
surge to 350 MLi by 2016.
The Biofuels Act or Republic Act (RA) 9367 was signed and mandated a minimum
one percent biodiesel blend in all diesel fuels by February 2007, and to increase to a two
percent blend after 2 years, and raise to 5 percent by 2015, 10 percent by 2020, and to 20
percent by 2030 (Corpuz, P., 2015) With this increase in demand in biodiesel, it is expected
that there would also be a noticeable increase in its production, and the generation of Crude
Glycerol as its waste. Table 2.1 presents the major biodiesel manufacturing plant in the
Philippines in 2011, and their corresponding capacity.
Table 2.1. Major Biodiesel Manufacturing Plant in the Philippines as of 2011
Source: Philippine Coconut Authority, 2011

Figure 2.2. Coconut Coir
Based on Philippine Statistics Authority, the Philippines produced 14,735,200 Metric

Tons (MT) of coconut in 2015. In the Philippines, the coconut palms are also called the “tree
of life” from the numerous products and by-products that could be derived from it. The major
coconut wastes include coconut shell (12%), coconut husks (35%) and coconut coir.
Table 2.2. Composition of various agricultural and other lignocellulosic residues
As presented in Table 2.2 above, coconut coir has the highest lignin content among
the various agricultural and other lignocellulosic residues having 41-45%.
Extraction of lignin from different bio sources used in this study was carried out using
a mixture of formic acid/acetic acid/water for pulping with the main objective of degrading
the lignin molecules by dissolving them in the solution and consequently retrieving by
washing them. Organosolv (acetic acid/formic acid) under acidic condition cleaves ether
bonds between lignin and hemicellulose, thereby accelerating the delignification process.
PROCESS
Liquefaction reaction
The acid liquefaction reactions were carried out in a 300 cm3 stainless steel vessel
(PARR, model 4566) equipped with an independent controller (PARR, model 4842), stirrer
(200 rpm), heating resistance (1000 W), internal water cooling system and temperature
sensor with the valves opened. The typical procedure consisted in introducing weighed
amounts of dried spent coffee grounds, solvent mixture (PEG 400/glycerol, 90/10 w/w) and
sulfuric acid (3 and 4 wt%) in the reactor. The concentration of sulfuric acid was calculated
as the weight content based on the amount of liquefaction solvent mixture. The reaction
mixture was then stirred at room temperature for 5 min allowing impregnation of the spent
coffee grounds with the solvents. The effect of temperature was studied between 150 and
170∘C for two reaction times: 60 and 80 min. Time countdown started when the
temperature of the reaction reached the defined set point. Following the same procedure,
the effect of reaction time was studied for the reaction times: 10, 20, 40, 60, 80, 100, 120,
150 and 180 min. At predefined reaction times, the heating system was turned off and the
stirrer kept running until the mixture cooled down to room temperature, using a cold-water
bath to quench the reaction. The polyols obtained upon recovery from the reactor were a
mixture of liquefied spent coffee grounds and a solid residue. In order to optimize the
liquefaction conditions (temperature, sulfuric acid concentration, and time) the liquefaction
solvents/spent coffee grounds ratio of 3/1 (w/w) and the solvent mixture PEG 400/glycerol
ratio of 90/10 (w/w) were fixed. These parameters were selected based on suitable values
found in previously published liquefaction studies for several other lignocellulosic
agricultural crop residues.11,13–17,20 All experiments and analyses were performed at

least in duplicate and the data are expressed as mean±standard deviation.
Determination of spent coffee grounds conversion ratio
Following the procedure reported by Hu et al.39 approximately 2 g of polyol

(liquefaction product with solid residue) were weighed and well dispersed in 30 mL of
ethanol in a 250 mL Erlenmeyer flask, at 30∘C, under magnetic stirring for 10 min. Then,
the solid residues were separated by vacuum-filtration using a 50 mL pre-dried fritted glass
filtering crucible with a layer of cellulose filter paper (grade 1,Whatman®) placed at the
bottom. Deionized water was used to rinse the residue in the crucible until the filtrate
became colorless. The crucible was dried in an oven at 105 ±2∘C for 24 h to ensure
complete drying. The biomass conversion was calculated using Equation (1).
Biomass conversion ratio (wt %) = 100 − [((W1 –W2) ∕W3) × W4 × 100] ∕W5 (1)
where W1 is the total dry weight of the filtering crucible with residue (g);
W2 is the net weight of filtering crucible without residue (g);
W3 is the weight of polyols’ sample (reaction product) used for the

determination of spent coffee grounds conversion ratio (g);
W4 is the total weight of polyols obtained from the liquefaction process

(reaction product) (g) and
W5 is the weight of spent coffee grounds used in the liquefaction process (g).
The biomass conversion ratio is the average value of at least two consistent
replicates (less than 5 wt% deviation).
SYNTHESIS OF POLYURETHANE
The polyol component and the corresponding amounts of catalyst (3 parts per polyol
wt/wt), surfactant (4 parts per polyol wt/wt) and blowing agent (6 parts per polyol wt/wt),
were placed in a polypropylene cup and homogenized using a mechanical stirrer for ca. 10
seconds at 700 rpm. Note that the amounts of water present in the polyols were subtracted
to the amounts of blowing agent added. Next, the appropriate amount of isocyanate to
obtain a RNCO/OH=1.10 (ratio between NCO groups of isocyanate and OH groups) was
added and the mixture homogenized again. The RNCO/OH values used in the PUFs
production were determined using Eq. 1.
Where
RNCO/OH is defined as the number of moles of NCO groups of the isocyanate per OH
moles of each polyol and water
miso is the mass (g) of isocyanate
%NCO is the quantity of NCO groups in the isocyanate (31.1%)
MNCO is the molecular weight of NCO group.
mpolyol is the mass (g) of each polyol
OHnumber and AV are the hydroxyl number and the acid value of each polyol
respectively (mgKOH.g-1).
MKOH is the molecular weight of KOH
mH2O is the mass of water present in each polyol
mBA is the mass of blowing agent (water) added
EqH2O is the equivalent of OH groups present in the water.
The values of OHnumber, AV and water content of the mixtures of polyols, were
determined by the contribution of each polyol.
POLYURETHANE AEROGEL SYNTHESIS
Polyurethane gels were synthesized through a sol–gel route based on polyaddition

reactions between polyols and polyisocyanates according to the following classical chemical
scheme for generic diol and di-isocyanate
The reactants were first dissolved in a suitable organic medium in which both
monomers and the growing polyurethane particles are soluble. It consists of a mixture of
dimethylsulfoxide and ethyl acetate (respectively noted DMSO and EtAc). The composition
(and the corresponding Hildebrand solubility parameter d) of the organic media of gelation
was varied by adjusting the volume fraction of DMSO in the mixture (XDMSO).
For this study, MDI (4,40-methylenebis(phenylisocyanate) from Elastogran,

commercialized under the name of Lupranat M20S) was used as the polyisocyanate
whereas two polyols with different functionalities – saccharose and pentaerythritol (noted
polyol A and polyol B, respectively) – were studied. For each type of polyol, different mass
concentrations of the solid in solution (ms) and different mass ratios between polyol and
MDI (mp) were used. The sol compositions were selected to keep mp and ms similar
between the two systems A and B. For 100ml of DMSO/EtAc mixture, systems A are
composed of 3.6g of MDI and 1g of polyol while systems B contain 5.4g of MDI and 1g of
polyol. To promote gelation, a commercial diamine catalyst (DABCO TMR from Air Products)
was slowly added to the mixture (0.5 vol.%) under slow mechanical stirring at room
temperature. For both systems A and B, gelation occurred within minutes. For comparison
purposes, both supercritical and subcritical drying processes were performed. In the
supercritical route (noted SCD), gels were directly washed with supercritical carbon dioxide
(5kgCO2h-1 at 37C and 82bar) before slow isothermal depressurization (0.05 barmin-1 at
37C) [13]. Simple evaporative drying (noted EVD) was performed at atmospheric pressure
below the normal boiling point of the interstitial solvent. Finally, a slow freeze-drying process
(noted FD) was also tested [14]. Prior to drying, specific washing steps of the gels were
performed depending on the drying route. The reaction media was replaced by a solvent
either highly soluble in CO2 or having a low surface tension at temperatures <100C (ethyl
acetate) for SCD and EVD routes, respectively, or presenting moderate triple-point
coordinates (cyclohexane) for the FD route. The SCD, EVD and FD drying routes produced
material
Supercritical Drying
Supercritical drying (SCD) is a process by which the liquid in a substance is

transformed into gas in the absence of surface tension and capillary stress. Furthermore,
SCD is the process most commonly used to convert gels into aerogels. It is performed to
replace the liquid in a material with a gas, isolate the solid component from the material
without destroying the material’s delicate pore network.
This process entails heating or pressurizing the liquid in a material past its critical
point, at which it is transformed into a supercritical fluid. As a liquid approaches its critical
point, the molecules in the liquid move past each other faster and faster and stick together
less, meaning the surface tension of the liquid decreases. Thus the capillary stress that the
liquid can exert decreases as well. At the critical point, the supercritical fluid loses all
surface tension and can no longer exert capillary stress. Thus, at this point, the supercritical
fluid can be removed from the pores of the material by depressuriziing the fluid while
keeping it above its critical temperature (isothermal depressurization). If the temperature of
the fluid drops below the critical temperature, liquid will start to rain out of the fluid. As
pressure is released from the vessel containing all of this, molecules are removed from the
fluid to the surroundings as a gas and the fluid becomes less dense. After a while, enough of
the fluid will have been removed from the pressure vessel so that when it is cooled below its
critical point there just isn’t enough substance to recondense to a liquid and instead reverts
to a gas.
PRODUCT
Aerogels are a diverse class of porous, solid materials that exhibit an uncanny array
of extreme materials properties. Most notably aerogels are known for their extreme low
densities (which range from 0.0011 to ~0.5 g cm-3). In fact, the lowest density solid
materials that have ever been produced are all aerogels, including a silica aerogel that as
produced was only three times heavier than air, and could be made lighter than air by
evacuating the air out of its pores. That said, aerogels usually have densities of 0.020 g cm-
3 or higher (about 15 times heavier than air).
Significant industrial interest exists with respect to the development of innovative

efficient materials for thermal insulation applications. Many research and development
studies have long focused on materials like aerogels because they are lightweight,
nanostructured mesoporous materials presenting very low effective thermal conductivity.
Most of these studies deal with inorganic silica aerogels or xerogels that can be considered
as superinsulating materials, but which have generally poor mechanical properties (Rigacci,
et al, 2004).
TESTING
Thermal Conductivity
Option 1: National Metrology Laboratory (NML)
The National Metrology Laboratory (NML) is the national metrology institute of

the Philippines tasked by law to be responsible for establishing and maintaining the national
measurement standards for physical quantities. It is located at the Metrology Building within
the Department of Science and Technology (DOST) Compound. The laboratory fee for the
thermal conductivity testing is Php 1400.00.
Option 2: University of the Philippines Diliman – Department of Mining, Metallurgical

and Materials Engineering
The Mining, Metallurgical and Materials Engineering Department of the University of

the Philippines Diliman offers a wide variety of testing facilities and machines which
includes the thermal conductivity meter.
Compressive strength and density
The Industrial Technology Development Institute (ITDI) of the Department of Science

and Technology offers a testing facility and machine for the compressive strength as well as
the density of the insulator through the ASTM C165 and ASTM C303 equipment,
respectively.

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PAMANTASAN NG LUNGSOD NG MAYNILA

University of the City of Manila

Chemocatalytic Conversion of Crude Glycerol

DIONISIO, Charles Amiel P.

June 14, 2017

CHAPTER II: Review of Related Literature and Studies

BACKGROUND OF THE STUDY

Crude glycerol is a by-product of the biodiesel which is considered to be a promising

Coconut coir is a by-product of the coconut palm processing. According to Philippine

Significant industrial interest exists with respect to the development of innovative

Polyurethane Aerogel Superinsulator is a special type of insulating material that is

STATEMENT OF THE PROBLEM

OBJECTIVES OF THE STUDY

The study also aims to achieve the following objectives:

 To devise an experimental method and determine the optimum operating conditions

SIGNIFICANCE OF THE STUDY

To the Students & Researchers

To the Chemical Engineering Profession

To the Biodiesel Producers

REVIEW OF RELATED LITERATURE AND STUDIES

Figure 2.1. Crude Glycerin or Crude Glycerol

digestion, animal feeds, and thermochemical/biological conversions to value-added

In this study, it is important to determine whether the raw material to be used is

Table 2.1. Major Biodiesel Manufacturing Plant in the Philippines as of 2011

Source: Philippine Coconut Authority, 2011

Figure 2.2. Coconut Coir

Based on Philippine Statistics Authority, the Philippines produced 14,735,200 Metric

Table 2.2. Composition of various agricultural and other lignocellulosic residues

agricultural crop residues.11,13–17,20 All experiments and analyses were performed at

Determination of spent coffee grounds conversion ratio

Following the procedure reported by Hu et al.39 approximately 2 g of polyol

W2 is the net weight of filtering crucible without residue (g);

W3 is the weight of polyols’ sample (reaction product) used for the

W4 is the total weight of polyols obtained from the liquefaction process

miso is the mass (g) of isocyanate

%NCO is the quantity of NCO groups in the isocyanate (31.1%)

MNCO is the molecular weight of NCO group.

mpolyol is the mass (g) of each polyol

MKOH is the molecular weight of KOH

mH2O is the mass of water present in each polyol

mBA is the mass of blowing agent (water) added

EqH2O is the equivalent of OH groups present in the water.

POLYURETHANE AEROGEL SYNTHESIS

Polyurethane gels were synthesized through a sol–gel route based on polyaddition

For this study, MDI (4,40-methylenebis(phenylisocyanate) from Elastogran,

Supercritical drying (SCD) is a process by which the liquid in a substance is

Significant industrial interest exists with respect to the development of innovative

Option 1: National Metrology Laboratory (NML)

The National Metrology Laboratory (NML) is the national metrology institute of

Option 2: University of the Philippines Diliman – Department of Mining, Metallurgical

The Mining, Metallurgical and Materials Engineering Department of the University of

Compressive strength and density

The Industrial Technology Development Institute (ITDI) of the Department of Science

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