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CHAPTER ONE

1.0 INTRODUCTION
With rapidly increasing environmental concerns, the stakes are exceedingly high for the search of
greener substitutes for various petrochemical products including fuels (Anand et al 2010). In this
context, the global biodiesel industry has recently experienced a major surge worldwide and has been on
an exponential growth curve over the past several years (Thompson et al. 2006). European Union
biodiesel board reported that the production capacity has currently reached some 22 million tones
[(European Biodiesel Board. 2009-2010)]. Some of the main drivers behind this tremendous growth are
reducing dependence on imported oil, environmental friendly alternative to diesel and reducing
greenhouse gas emission. However, there is almost the unanimous opinion among both proponents and
skeptics that the potential of the biodiesel requires attention to both safety and economic issues. The
global biodiesel market is estimated to reach 40 billion gallons by 2017 with an average annual growth
of 45%which means about 4 billion gallons of crude glycerol will be produced (Wang, 2006). Because
of this, glycerol stemming from biodiesel production is flooding the market. Finally the euphoria once
associated with biodiesel production has given way to disappointment because of lack of economic
viability as enormous amount of waste glycerol generated in its preparation (Saxena, 2009) At present,
most of it is disposed off in rivers or simply incinerated, making biodiesel a grey fuel rather a green fuel.
Although glycerol valorization has much to offer in reducing the cost of the overall biodiesel production
process in spite of the continuous efforts the realization of this vision is difficult to achieve. This is
because of the several impurities present in the crude glycerol such as residual methanol, NaOH, carry-
over fat/oil, some esters, and low amounts of sulfur compounds, proteins, and minerals (Celik & al,
2008)This has not only been a serious handicap in itself for being cost effective, but also served as a
major drag in the development of new alternative fuels that can be added to the limited armory of green
fuels. Thus, valorization of this low value crude glycerol into value added products via microbiological
or chemical routes currently attracts much and continuously increasing interest (Johnson, Taconi, &
K.A, 2007)

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1.2 STATEMENT OF THE PROBLEM
With increase in biodiesel production worldwide, crude glycerol, the biodiesel by product has increased
in a high quantity and is becoming a problem to biorefneries because they spend much in disposing
some of this byproduct as waste. In this work an effort was made to refine this glycerin from the waste.

1.3 AIMS AND OBJECTIVES


The aim of this research project is to produce pure glycerol as a value added product from biodiesel by-
product (glycerol). This can be achieved through the following objectives.

1. Extraction of glycerol from biodiesel byproduct.

2. Purification of glycerol and removal of impurities like methanol and alkaline.

3. Discoloration of glycerol with activated carbon to obtain pure glycerol.

1.4 SIGNIFICANCE OF THE STUDY

The importance of this research is to utilize crude glycerol into value added products and to reduce the
cost of disposing biodiesel waste by biorefineries. This will generate more revenue to the biodiesel
producers from the income realized in glycerol market, to Increase the production of biodiesel so that
more glycerol can be produced since it is an important raw material for production of other materials
like animal feed, cosmetics, soap and cream.

1.5 SCOPE OF THE STUDY

This project research is a bench scale laboratory production of pure glycerol from crude glycerol
(biodiesel byproduct).

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CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 INTRODUCTION
Glycerol, also referred to as glycerin or glycerine, is a chemical compound that is a generally nontoxic,
sweet-tasting viscous liquid. When we say viscous, this term means that the substance is a liquid with a
thick and sticky consistency. The formula for glycerol is C3H8O3. It has 3 carbon (C) atoms, 8
hydrogen (H) atoms, and 3 oxygen (O) atoms. In this image, you can see the appearance of glycerol and
its chemical formula and structure.

Figure 2.1

The chemical structure of glycerol shows that each carbon atom is bonded to an -OH group. These -OH
groups are what we call hydroxyl groups. Because of this, glycerol is classified as a polyol, which is an
alcohol containing more than one hydroxyl group. Glycerol is soluble in water because of the hydroxyl
(-OH) groups attached to the carbon atoms. These hydroxyl groups are also responsible for the
hygroscopic nature of glycerol, which means that it readily retains or takes up water. The density of
glycerol is 1.261 g/ml. Its boiling point is 290 degrees Celsius, and its melting point is 17.8 degrees
Celsius. These values show that glycerol is denser than water (because water has a density of 1 g/mL),
its boiling point is higher than water (water has a boiling point of 100 degrees Celsius), and its melting
point is higher than water (water has a melting point of 0 degrees Celsius).

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Glycerol is derived from natural or petrochemical feedstocks, which is produced as a by-product from
saponification and hydrolysis reactions in oleo chemical plants as well as trans-esterification reaction in
biodiesel plants. Disposal of crude glycerol is costly, it become useful to undergo purification process to
generate income. Demand of biodiesel production is increasing continuously has resulted in a large
surplus of glycerol and partially purified glycerol in the environment. To increase the economics of
biodiesel production, crude glycerol disposal and its utilization has become serious issue and a financial
and environmentally suitable for biodiesel industry. For the sustainability of biodiesel industry,
economic utilization of crude glycerol for value added products are critically important and the recovery
and purification of glycerol play an important role in biodiesel cost reduction.

Many conventional techniques for removal of impurities from crude glycerol have emerged such as
distillation and ion-exchange. The distillation is the most commonly practiced method for purifying
glycerol. The advantages of the distillation process are well known. However, the distillation of glycerin
is an energy-intensive process. Glycerol has a high heat capacity, which demands a high-energy input
for vaporization. Similarity ion-exchange techniques have also long been applied to glycerin
purification. However, the high salt content of glycerin issued from biodiesel production makes ion-
exchange uneconomical for this application. Specifically, the chemical regeneration cost for the resins
becomes exceedingly high when salt contents approach the 5-7%; which is the percent-range commonly
found in the biodiesel industry. Activated carbon has been the most popular and widely used adsorbent
in wastewater treatment applications throughout the world. This is due to its high adsorption capacity,
high surface area, microporous structure and high degree of surface reactivity (Babel and Kurniawan,
2003; Ozcan et al., 2004). In spite of its prolific use, activated carbon remains an expensive material
since the higher the quality of activated carbon, the greater it costs. Therefore, it not attractive to be used
in small-scale industries because of cost inefficiency. Hence, research interest into the production of
alternative adsorbent to replace the costly activated carbon has intensified. In recent years, of the many
sort of biosorbents recently investigated for the biosorption ability of heavy metals, Saccharomyces
cerevisiae has proven to be the most promising as well as reliable and (Chen and Wang, 2008). Lately,
the usage of dead bacterial cells for heavy metals removal has emerged as an alternative, since living
cells have their own inherent limitation such as less efficiency and sensitive operating conditions (Chen
and Wang, 2008; Farooq et al., 2010). It was found that various functional groups present on their cell
wall offer certain forces of attractions for the metal ions and provide a high efficiency for their removal.
Use of dead materials has several advantages because there is no need of growing, no growth media is

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required and these materials are available as wastes or by-products (Farooq et al., 2010). The free
bacterial cells are generally very small particles, with low density, poor mechanical strength and little
rigidity. These cells may pose several problems such as solid liquid separation, possible biomass
swelling and inability to regenerate/reuse. These problems can be avoided by the use of immobilized cell
systems. The immobilization of the biomass in solid structures would create a biosorbent material with
the right size, mechanical strength, rigidity, porosity and minimal clogging under continuous-flow
conditions, which are important factors necessary for use in practical processes (Hasan and Srivastava,
2009; Zhou et al., 2009; Wang and Chen, 2006; Wang and Chen, 2009). In this study, the uptake of
impurities by some Saccharomyces cerevisiae as a biosorbent was carried out. The main objective of this
study was to investigate the new processes for purification and recovery of glycerol through uptake of
impurities from the crude glycerol, a by-product of biodiesel production by nonliving Saccharomyces
cerevisiae biomass immobilized on chitosan. The main focus will be to possibilly improve the efficiency
of the impurities uptake from the crude glycerol by S. cerevisiae through pretreatment, immobilization
and the use of microwave irradiation.

2.2 DESCRIPTION OF GLYCEROL


Glycerol also known as Glycerin or propane-1-2-3-triol is a chemical that consists of three-carbon chain
with a hydroxyl group attach to each carbon. It is a clear, colorless, odorless, viscous liquid that is
widely used in pharmaceutical and manufacturing industries. It is hygroscopic in nature and highly
soluble in water. It is a sweet-testing and non-toxic substance. Crude glycerol is 7080% pure and is
often concentrated and purified prior to commercial sale to 95.599% purity. Crude glycerol contains
impurities such as alcohol, spent catalyst, ash, water, and fatty acid that barely differ from crude glycerol
in their physical properties. The appropriate composition of a typical crude glycerol derived from trans-
esterification, saponification and hydrolysis reaction of fat and oils. The dramatic increase in demand for
transportation fuels and the increase in environmental concerns, coupled with diminishing crude oil
reserves, have increased the emphasis on renewable energy. 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. Although world biodiesel production was expected to reach a high capacity,
in fact, it is less than the anticipated target and has increased at a slower rate. The main reason is its
relatively high production cost. Utilization of the glycerol co-product is one of the promising options for
lowering the production cost. Biodiesel production will generate about 10% (w/w) glycerol as the main
byproduct. In other words, every gallon of biodiesel produced generates approximately 1.05 pounds of
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glycerol. This indicates a 30-million-gallon per-year plant will generate about 11,500 tons of 99.9
percent pure glycerin. It was projected that the world biodiesel market would reach 37 billion gallons by
2016, which implied that approximately 4 billion gallons of crude glycerol would be produced. Too
much surplus of crude glycerol from biodiesel production will impact the refined glycerol market. For
example, in 2007, the refined glycerols price was painfully low, approximately $0.30 per pound
(compared to $0.70 before the expansion of biodiesel production) in the United States. Accordingly, the
price of crude glycerol decreased from about $0.25 per pound to $0.05 per pound. Therefore,
development of sustainable processes for utilizing this organic raw material is imperative. Since purified
glycerol is a high-value and commercial chemical with thousands of uses, the crude glycerol presents
great opportunities for new applications. For that reason, more attention is being paid to the utilization of
crude glycerol from biodiesel production in order to defray the production cost of biodiesel and to
promote biodiesel industrialization on a large scale. Although intensive investigations have focused on
utilizing crude glycerol directly, review papers on crude glycerol utilization are scarce. This review
mainly addresses the current and potential value-added applications of crude glycerol from biodiesel
production. Any discussion on glycerin and its market has to start by taking a look at the sources. This
will help shed more light on processes involved such as the purification processes before glycerin gets to
the market. The primary sources of glycerin are fats and oils and looking into their makeup will give a
better understanding of glycerin as a whole. As mentioned earlier there are other sources of glycerin
such as synthetic glycerin which is glycerin manufactured from non-triglyceride sources. But, this thesis
will be mostly centered on natural glycerin from seed triglycerides. The glycerol molecule is attached to
three fatty acids molecules in fat or oil forming triglycerides. The glycerol molecule is liberated as
byproduct during the breaking down of the triglyceride molecule. The processes that make use of
triglycerides as their primary raw material includes: trans-esterification for the production of biodiesel,
saponification for the production of soap, fat splitting for the production of fatty acids, etc. In these
processes the triglycerides reacts with other components and in some instances a catalyst is needed to
expedite the reaction. This chapter will focus more on glycerin sources fat and oil, the processing, how
glycerin is contaminated with impurities, the types of impurities, and possibly how best these impurities
could be avoided so as to save cost on glycerin purification.

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2.3 FATS AND OILS MAIN SOURCE OF GLYCERIN

Fats and Oils are triglycerides, tri-esters of glycerol that is three molecules of fatty acid attached to one
molecule of glycerol. They belong to a group called Lipids. Lipids are composite molecules, and they
are less dense than water and are insoluble in water and only soluble in organic solvent. The insolubility
in water is due to almost all the bonds being non-polar carbon to hydrogen or carbon to carbon. fat and
Oil are similar in that fat has long fatty acid chains and could be solid at room temperature while oil
have short fatty acid chains and are liquids at room temperature. Fig. 2.1 shows the molecular structure
of triglyceride, the major component of fats and oils. The three molecules of fatty acids have a common
backbone which is glycerol molecule. Ra, Rb and Rc are long fatty acid chains that contain carbon and
hydrogen atoms. Soybeans oil is used mostly often for production of biodiesel in US. It has five main
fatty acids: linoleic, linolenic, oleic, palmitic and stearic.

Fig.2.2 Molecular Structure of Fat and Oil

2.4 THE GLYCEROL SIDE PRODUCT

Produced in a 1:3 molar ratio and 1:10 mass ratio with biodiesel is glycerol. Glycerol is a polyol, a sugar
alcohol, with three carbons and three hydroxyl groups. It is hygroscopic, meaning it can absorb water,
and is also soluble in water. It melts at 17.8oC, boils at 2900C, and is viscous.

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Figure 2.3: The structure of glycerol

2.5 DEFINITION OF BIODIESEL


Biodiesel is a renewable, biodegradable and environmentally safe fuel for use in diesel engines that can
be produced from vegetable oils, animal fats and/or used cooking oils via alcohol trans-esterification. It
is comprised of fatty acid alkyl esters (FAAE). It can be used in its neat form or as a blend with
conventional diesel fuel. The similarities between biodiesel and diesel fuel show that biodiesel is a
successful alternative source of energy in diesel engines (Demirbas, 2003).

2.5.1 Production of Biodiesel


The main feedstock used in biodiesel production is vegetable oil. The idea of running an engine on
vegetable oil has existed ever since the invention of diesel engine. In 1893, Rudolf Diesel the inventor of
the diesel engine showed that diesel engine could be operated on vegetable oil by successfully using
peanut oil (suwannakarn, 2008)). But, the high viscosity of vegetable oil over conventional diesel was a
problem. The blending of vegetable oil with conventional diesel was not an option because of decrease
in power output and thermal efficiency. To take care of this viscosity problem, trans-esterification which
is the transformation of an ester into another ester was a solution. This lowers the viscosity of vegetable
oil derived diesel called Biodiesel and make it is compatible in a modern engine. Biodiesel is defined as
a mono-alkyl ester fuel comprised of long chain fatty acids obtained from triglycerides. B100 implies
100% biodiesel which could be used to run diesel engine without making much alteration in the engine.
It could be blended with conventional diesel. B20 is a 20% biodiesel blend with 80% conventional
diesel. Biodiesel has become more attractive because of increase in cost of conventional diesel; renew
able sources, environmentally friendly, high performance, etc. In the production of biodiesel, the type of
raw materials to be used is purely based on chemistry and economic options. The primary reactants are
fats or oils and alcohol; other components are catalyst and neutralizer.

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Figure 2.4: Overall reaction of triglycerides with methanol to form biodiesel and glycerol

2.5.2 PRETREATMENT OF WASTE COOKING OIL AS FEEDSTOCK

Waste cooking oil (WCO) is the oil obtained after using the edible oil for frying. The amount of WCO
generated at homes and restaurants is increasing exponentially as a result of tremendous growth in
human population (al., 2009)Despite the changes that occur during frying, WCO is a good option as
feedstock for biodiesel production, once it is treated by being free of unwanted materials (al. K. e.,
2006)The chemical reactions that occur during frying process (depending on level and condition of
usage) include oxidative and thermolytic reactions, result in the formation of oxidation derivations
composing of various acids and polymerized materials (Issariyakul, 2011). These resulted into increase
in acid value and oxygen content of the used cooking oil. WCO contains unwanted contents such as
FFA, water and other solid impurities. The presence of water in oil sample often leads to hydrolysis and
high FFA content leads to saponification. Both reactions results in low biodiesel yield and catalyst
consumption (al, 2013). To reduce the high FFA content in oil, several techniques have been proposed,
such as acid esterification with methanol and sulphuric acid, esterification with ion-exchange resins,
neutralization with alkalis followed by soap removal, and extraction with polar liquids along with acid
esterification and distillation of FFA (Cvengros, 2004)To remove water present, WCO is heated to
temperature above 100 0C. Vacuum distillation (0.05 bar) is used at the industrial scale. And suspended
solids and other impurities can be removed by centrifugation and filtration (Chen et. al., 2009).

2.5.3 Glycerol Separation

Separation of glycerol from biodiesel (desired product) is very important, being the first step in

Obtaining pure biodiesel and also to avoid possible reversible process. Glycerol can cause clogging of
injectors and carbon residues in the engine if not completely removed (Lamers, 2010) The common

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laboratory practice of glycerol removal is decanting using a separating funnel. After about 24 hours of
allowing trans-esterification products separate to a clear light (biodiesel) phase and a denser phase
(glycerol) are obtained (Erickson, 2002). There is often a quality control check, for if there is no distinct
separation (but emulsion or soap formation), then problems may have occurred during reaction as a
result of any (or combination) of the followings: insufficient/excess usage of methanol or/and catalyst,
extreme high/low reaction.

2.5.4 Glycerol Purification

The glycerol phase resulting from biodiesel production is usually of low quality. The glycerol content
itself is generally between 60-80 percent, and contains most of the unreacted methanol and the catalyst.
It is a dark brown color. The glycerol that is used as a feedstock to processes is generally of very high
concentration, with USP grade being between 96 and 99.5 percent. Kosher grade requires at least 99.5
percent pure (al A. e., 2012)Purification is a necessary step if the glycerol is to be sold, and there are
several methodologies employed to achieve these high concentrations. The crude glycerin obtained
from the recovery process still needs to undergo refining processes to get a better market value. The
impurities in glycerin come from the process that it passed through during the production processes and
the feed stock used. These impurities include: salt, soap, matter organic non glycerin (MONG), water,
color pigments, odor, etc. To get a better value, glycerin undergoes further purification processes where
impurities are removed. The crude glycerin market is volatile because of large volume pumped into the
market by fat splitting and, of late, biodiesel production. The refined glycerin market is stable, with even
the United States importing refined glycerin to meet up with demand. Glycerin refining is costly but,
when refined the high market prices offset the production and refining cost. There are many methods of
refining glycerin including vacuum distillation, ion exchange, electrolysis, ion exclusion, etc. The use of
activated carbon promotes stability and it is used at the range of 0.5 to 1.0%. The carbon column is made
of three operational columns in series and one standby and they are filled with dry activated carbon. To
saturate the carbon and displace air, water or heated distilled glycerin at 75 0C to 85 0C is used to fill the
column and this is allowed to settle and is vented to atmosphere. This ensures proper saturation and all
air is removed to prevent channeling of glycerin through carbon beds; this will prevent poor glycerin
output and excessive use of carbon.

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2.5.5. Effect of Activated Carbon Quantity on Adsorption

The effect of amount of activated carbon used during adsorption process is of interest because the use of
activated carbon plays a very important role on the color of glycerin obtained. To determine this effect
an experiment was conducted by (Manosak, 2011), in which different ratios of activated carbon and
glycerin were used. The literature shows the result obtained on the color, glycerin and ash content of
refined glycerin. The amount of activated carbon was varied from 40g/l glycerin to 200g/l glycerin, of
the three areas of concern the effect was noticed more on the color which is the main reason of using
activated carbon.

2.5.6. Features of Refined Glycerin

The essence of refining glycerin is to impart better quality on the glycerin molecules by removing some
unwanted impurities which got associated with it during processing. This improves its appearance,
applications, market value, etc. Some of the features of refined glycerin are contained in this section.

Viscosity

One noticeable feature of refined glycerin is its viscosity which when compared to that of crude glycerin
shows clear impact of refining on glycerin mixture. In order to examine this, an experiment was
conducted on the viscosity of crude and refined glycerin (Kovacs, 2011). Figures 4.10, 4.11 and 4.12
shows results of viscosity test on the crude glycerin partially refined and complete refined glycerin. The
viscosity profile of crude glycerin tends to curve downward which indicates the presence of
microscopically dispersed impurities that is evenly dispersed in crude glycerin.

Figure. 2.3 viscosity Profile of Crude Glycerin (Kovacs, 2011)

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The viscosity of crude glycerin is about 15 times more than that of refined glycerin even with increase in
temperature and velocity gradient (Kovacs, 2011).

The refining of crude glycerin tends to reduce high viscosity and the level of refining determines the
amount of resistance to flow that is obtained.

Mass Spectrum

The spectrum of refined glycerin is slightly distinct from partially refined glycerin and greatly distinct
from that of crude glycerin. These distinct differences can be seen by a look at the spectra of different
grades of glycerin. Figures 2.4 show spectra of different grades of glycerin from an experiment that was
conducted by (al M. e., 2011). The crude glycerin that was used for this experiment was obtained from
waste oil biodiesel plant. A look at the spectrum shows glycerin at 42.879%, alcohol (methanol and
isopropanol) and fatty acids that are replica of fatty acids found in original triglyceride that was used for
biodiesel formation.

Figure. 2.4. Mass Spectrum of Crude Glycerin (Manosak, 2011)

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Ion Exchange

Another refining method for glycerin is ion exchange. This method is simple and energy consumption is
low causing it to gain attention. The process of ion exchange is the exchange of ions between liquid
crude glycerin mixture and solid ion exchange material. This process is reversible and there is no
permanent change in the solid receiving the unwanted ion. Commonly used ion exchange resins are
made of cross-linked polymer matrix with good ion active sites. Ion exchange beads are mostly
spherically shaped.

Color

The color of a refined glycerin is clear water color. This is a sharp contrast from crude glycerin which is
light brown because of presence of the triglycerides color pigments. This color can be removed
completely during refining by bringing the activated carbon in contact with the glycerol.

Ash Content and Odor

The refining of glycerin reduces the ash content to a limited value. The ash content is mostly leftover
salts and inorganic components. Refined glycerin is odorless because some of the odor causing
impurities has been removed as a result of refining. The best option to add value to crude glycerin is to
refine it. This will help reduce the stress associated with disposing crude glycerin obtained from
producing biodiesel, fatty acids, soap, etc. The demand for glycerin has been stable but, the market has
witnessed oversupply because of biodiesel production and this makes the market very volatile. There are
many applications of glycerin but, mostly these applications use technical grade glycerin which has a
concentration of 98% or more and the only way to achieve that is by refining. Many methods are used
for the refining of crude glycerin but, vacuum distillation and ion exchange are so far the best option.
Vacuum distillation appears to be widely accepted but the cost of operation is a huge minus and that has
made ion exchange an option. Ion exchange has its own flaws of being selective and requiring
regeneration. Despite the shortcoming of these processes the most important thing is that a byproduct
was transformed into value product. This will help biodiesel manufacturers who are struggling with
production costs to reduce the cost of their operation.

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2.6 GLYCERIN APPLICATION
The application of glycerin is noticed in almost every aspect of life from pharmaceuticals and foods to
cosmetics and technical industries. There are about 2000 known applications of glycerin (Glycerine and
the market, n.d.). The Global Industrial Analyst Inc. (a market research company) projected that global
consumption of glycerin will reach 5.4 billion pounds by 2017 (Global glycerin market to reach 5.4b,
2012). Glycerin is a very relevant olechemical and the abundant availability of this chemical in crude
form has attracted low price and has sparked the drive to discover more uses for it. The wide
applications of glycerin are due to a combination of factors like the physical and chemical properties
such as viscosity, high boiling point, hygroscopic nature, nontoxic, etc. The compatibility of glycerin
has made it a chemical of choice in many applications, in this research a look at some areas of
applications will help illustrate the importance of glycerin.

2.6.1. Food and Feed

Glycerin when used as food component is digested easily as a carbohydrate. It is found as a component
in foods, dessert, wine, milk, candies, gums, etc. It has a sweet taste as mentioned earlier and used as a
sugar substitute but contains no sugar. It is 60% as sweet sucrose and a teaspoon serving contains 27
kilo calories (Refined glycerin, n.d.). One good thing about glycerin is that it does not cause cavities,
because the plaques that cause cavities do not feed on it.

2.6.2 Pharmaceutical and Personal Care

Glycerin is used extensively in the manufacturing of drugs although in small amounts and it is used to
provide lubrication, smoothness and as humectants to improve moisture retaining ability. In solid drugs
it is used as a drug coating, it is used in laxatives, cough syrups, expectorants, etc. Glycerin is used as a
health supplement; this is because it regulates body temperature by lowering core body temperature
when hot. It delays dehydration in hot environment by increasing the volume of blood. In personal care
products it is used in manufacturing of mouthwash, toothpaste, creams, hair and skin care products,
soap, etc. When used in these areas it used as an emollient, solvent, lubricant, humectants, etc. Glycerin
can be used in place of propylene glycol or sorbitol.

2.6.3 Botanical extracts

When utilized in "tincture" method extractions, specifically as a 10% solution, glycerol prevents tannins
from precipitating in ethanol extracts of plants (tinctures). It is also used as an "alcohol-free" alternative

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to ethanol as a solvent in preparing herbal extractions. It is less extractive when utilized in a standard
tincture methodology. Alcohol-based tinctures can also have the alcohol removed and replaced with
glycerol for its preserving properties. Such products are not "alcohol-free" in a scientific sense, as
glycerol contains three hydroxyl groups. Fluid extract manufacturers often extract herbs in hot water
before adding glycerol to make glycerites. When used as a primary "true" alcohol-free botanical
extraction solvent in non-tincture based methodologies, glycerol has been shown to possess a high
degree of extractive versatility for botanicals including removal of numerous constituents and complex
compounds, with an extractive power that can rival that of alcohol and water alcohol solutions. That
glycerol possesses such high extractive power assumes it is utilized with dynamic methodologies as
opposed to standard passive "tincturing" methodologies that are better suited to alcohol. Glycerol
possesses the intrinsic property of not denaturing or rendering a botanical's constituents inert (as
alcohols i.e. ethyl (grain) alcohol, methyl (wood) alcohol, etc., do). Glycerol is a stable preserving agent
for botanical extracts that, when utilized in proper concentrations in an extraction solvent base, does not
allow inverting or reduction-oxidation of a finished extract's constituents, even over several years. Both
glycerol and ethanol are viable preserving agents. Glycerol is bacteriostatic in its action, and ethanol is
bactericidal in its action.

2.6.4 Electronic cigarette liquid

Vegetable glycerin is a common component of e-liquid, a solution used with electronic vaporizers
(electronic cigarettes). This glycerol is heated with an atomizer (a heating coil often made of Kanthal
wire), producing the aerosol that delivers nicotine to the user.

2.6.5 Antifreeze

Like ethylene glycol and propylene glycol, glycerol is a non-ionic kosmotrope that forms strong
hydrogen bonds with water molecules, competing with water-water hydrogen bonds. This disrupts the
crystal lattice formation of ice unless the temperature is significantly lowered. The minimum freezing
point temperature is about 36 F (38 C) corresponding to 70% glycerol in water.

Glycerol was historically used as an anti-freeze for automotive applications before being replaced by
ethylene glycol, which has a lower freezing point. While the minimum freezing point of a glycerol-water
mixture is higher than an ethylene glycol-water mixture, glycerol is not toxic and is being re-examined
for use in automotive applications.

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In the laboratory, glycerol is a common component of solvents for enzymatic reagents stored at
temperatures below 0 C due to the depression of the freezing temperature. It is also used as a
cryoprotectant where the glycerol is dissolved in water to reduce damage by ice crystals to laboratory
organisms that are stored in frozen solutions, such as bacteria, nematodes, and mammalian embryos.

2.6.6 Internal Combustion Fuel

Glycerol is also used to power diesel generators supplying electricity for the FIA Formula E series of
electric race cars.

2.6.7 Chemical Intermediate

Glycerol is used to produce nitroglycerin, which is an essential ingredient of various explosives such as
dynamite, gelignite, and propellants like cordite. Reliance on soap-making to supply co-product glycerol
made it difficult to increase production to meet wartime demand. Hence, synthetic glycerol processes
were national defense priorities in the days leading up to World War II. Nitroglycerin, also known as
glyceryl trinitrate (GTN) is commonly used to relieve angina pectoris, taken in the form of sub-lingual
tablets, or as an aerosol spray. Allyl iodide, a chemical building block for polymers, preservatives,
organometallic catalysts, and pharmaceuticals, can be synthesized by using elemental phosphorus and
iodine on glycerol. A great deal of research is being conducted to try to make value-added products from
crude glycerol (typically containing 20% water and residual esterification catalyst) obtained from
biodiesel production. The use of crude glycerol as an additive to biomass for a renewable energy source
when burned or gasified is also being explored.

Hydrogen gas production unit

Glycerine acetate (as a potential fuel additive)

Conversion to propylene glycol

Conversion to acrolein

Conversion to ethanol

Conversion to epichlorohydrin, a raw material for epoxy resins

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2.6.8 Film Industry

Glycerol is used by the film industry when filming scenes involving water to stop areas from drying out
too quickly.

2.6.9 Ultrasonic couplant

Glycerol can be sometimes used as replacement for water in ultrasonic testing, as it has favorably higher
acoustic impedance (2.42MRayl vs 1.483MRayl for water) while being relatively safe, non-toxic, non-
corrosive and relatively low cost.

2.6.10 Vibration dampening

Glycerol is used as fill for pressure gauges to dampen vibration. External vibrations, from compressors,
engines, pumps, etc., produce harmonic vibrations within Bourdon gauges that can cause the needle to
move excessively, giving inaccurate readings. The excessive swinging of the needle can also damage
internal gears or other components, causing premature wear. Glycerol, when poured into a gauge to
replace the air space, reduces the harmonic vibrations that are transmitted to the needle, increasing the
lifetime and reliability of the gauge.

2.6.11 Industrial Chemicals

The surplus availability of crude glycerin has made the conversion of crude glycerin into any chemical
of choice a common practice. Some factors considered in deciding which chemical option are: cost of
the conversion, price and demand of chemical of choice in the market. Chemicals of options are for
example propylene glycol, epichlorohydrin, propanol, isopropanol, acrolein, acrylic acid and polyol. All
have higher value than glycerin. Two chemicals will be discussed which will likely have an impact on
glycerin market.

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CHAPTER THREE

3.0 MATERIAL AND METHOD

3.1 MATERIALS
Crude glycerol was obtained from the department of chemical engineering laboratory university of
Maiduguri, liquid at room temperature. All chemical (sulphuric acid, Tetraoxosulphate (VI) acid (H
2SO4) etc.) were obtained from chemical engineering laboratory. The major equipment used are
presented in Table 3.1.

Table 3.1: Major equipment used in the Experiment

Name Model Manufactured

1. Beaker 250 & 500ml TECHMEL

2. Conical flask 250ml TEKK USA

3. Separation funnels etc. 250ml TEKK USA

4. Magnetic heat stirrer 250ml TEKK USA

5. Digital scale 250ml TEKK USA

6. Digital PH meter 0.01-1000g Enkay enterprises

3.21.1. METHODS

Crude glycerol under ambient temperature was measured and the PH was recorded. The crude glycerol
was added to a 500ml beaker. A 25% molar excess of 96% sulfuric acid was added to a desired PH level
of 7.0, and the reaction mixture was stirred for 1 hour on a magnetic stirrer as shown in fFigure.3.1. The
reaction mixture was transferred into a separation funnel as shown as in figFigure. 3.2. After standing

18
for a requisite time, the material was separated into 3 distinct layers; top-methyl esters, middle-glycerin,
bottom-salt. The top phase was separated by simple decantation. The fatty acid phase was separated
from the glycerol rich phase using a separating funnel. The extract glycerol was neutralized using 12M
KOH solution followed by evaporation of water at 1100C for two hours and filtered to remove the
precipitated salt. The glycerol obtained was further purified by solvent extraction process using
methanol as solvent to promote the precipitation of dissolved salts. The precipitated salts were separated
via filtration and the glycerin was passed through a column of activated carbon to decolor and remove
odor and some metal ions, in the experimental processes.

Characterization of crude and purified glycerol


The crude and purified glycerol samples were characterized for the density, alkalinity, moisture content,
glycerol content, ash content, metal content and the color intensity.
Density
The density was determined according to ASTM D 891-95 (2004). First, the weight of the dried
pycnometer was recorded. Water was added into the pycnometer at room temperature (22 1C) and its
mass and hence the volume of the pycnometer was recorded. Again, crude or purified glycerol was filled
in the dried pycnometer at same temperature and the mass of the crude glycerol was reported. The
density of the crude glycerol was obtained by taking the ratio between the mass of the sample and the
volume of the pycnometer.
Ash Content
Ash content was analyzed according to standard method ISO 2098-1972 by burning 1 g of glycerol in
muffle furnace at 750C for 3h.
pH
Around 1.00 g of crude or purified glycerol was dissolved in 50.0 ml of deionized (DI) water. The pH of
the solution was measured by a pH meter (SymphonyTM 89231-608, VWR) at room temperature (22
1C) after calibration of the apparatus with buffer solutions of pH 7 and 10.
Water content
The water content of crude or purified glycerol was measured following the standard method ISO 2098-
1972 by using the Karl- Fisher titrator V20

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Figure 3.1 The 3 layers formed by the addition of sulphuric acid at temperature above 30c

Figure 3.2. The layer of FFA and glycerol

20
CHAPTER FOUR

4.0 RESULTS AND DISCUSSION


The result of the research or findings is to compare the properties of commercial grade glycerol with
cooking oil biodiesel glycerol.

Table 4.1. Comparison of purified glycerol, crude waste glycerol and commercial grade glycerol.

S/NO Parameters Crude Glycerol Commercial Purified

1 PH 10.2 7.0 7.4

2 Ash Content (wt %) 3.9 0.002 0.009

3 Water Content (wt %) 13.5 0.001 9.68

3 Density @ 30o C (g/cm3) 1.014 1.267 1.089

4 Viscosity @ 40 oC (cst) 267.7 46.8 134.9

5 Color Dark brown Clear Pale light brown

4.2 DISCUSSION OF RESULTS


Recovered crude glycerol was a by trans-esterification process of waste cooking oil into biodiesel
(methyl ester) obtained from the chemical engineering laboratory University of Maiduguri. The obtained
crude glycerol is a thick liquid with high alkaline pH (10.2) compared with commercial glycerol found
to contain with a high content of ash, water and contaminants and with lower density and viscosity
compared with the commercial pure glycerol. The Table above shows the comparison of characteristics
of crude glycerol obtained from biodiesel by-product with the commercial glycerol.

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COLOR Formatted: Font: Bold

The color of a refined glycerin is clear water color. This is a sharp contrast from crude glycerin which is
light brown because of presence of the triglycerides color pigments. This color can be removed
completely during refining. The effect of amount of activated carbon used during adsorption process is
of interest because the use of activated carbon plays a very important role on the color of glycerin
obtained. To determine this effect the purified glycerol was contacted with an activated carbon to reduce
the darker color of the crude glycerol to brighter color. It was noticed that there was more change on the
color which is the main reason of using activated carbon. The color of the glycerol solution was reduced
drastically after this purification stage, but was still not clear, having a rather light brown tint. This
might be attributed to the presence of some minor amounts of saturated fatty acids, as well as other
unknown compounds. Also the color differs due to different biodiesel feedstock

VISCOSITY

One noticeable feature of refined glycerin is its viscosity which when compared to that of crude glycerin
shows clear impact of refining on glycerin mixture. The viscosity of crude glycerin is about 15 times
more than that of refined glycerin even with increase in temperature and velocity gradient. The refining
of crude glycerin tends to reduce high viscosity and the level of refining determines the amount of
resistance to flow that is obtained. From the viscosity profile of partially refined glycerin, the resistance
to flow tends to increase at the beginning and tends to normalize as the velocity gradient is increased.
This reduction to resistance to flow results from moving microscopic dispersed impurities thereby
causing applied shear stress to meet with lesser strain. It can be seen that viscosity of glycerin is a
function of temperature because as the temperature increase the resistance to flow tends to reduce.

ASH CONTENT

The purification of glycerol reduces the ash content to a limited value as can be seen from findings of
this research. The ash content is mostly leftover salts and inorganic components. The pH of the purified
glycerol is directly related to the ash content of sample.

PH

The results revealed that addition of acid reduced the pH of waste stream glycerol from a highly alkaline
to a near acidic pH which helps the microbes to utilize waste glycerol for bioconversions when added

22
with other nutrients. In acidification process the soluble soap was converted to insoluble free fatty acid
which floats at the top layer. The remaining ions coupled with the catalyst used in biodiesel production
precipitate and settle at the bottom layer as contaminant salt. But a further increase of pH value would
concomitantly decrease the glycerol yield. However, a too strong acidic condition may only corrode the
equipment and promote the esterification reaction of glycerol with acid, resulting in low glycerol yield.

WATER CONTENT

The water content of the purified glycerol might be attributed to absorption of moisture from the
surrounding during the transesterification process. Glycerol is hygroscopic and can absorb water from
the surrounding.

DENSITY

The density was determined first, the weight of the Beaker was recorded. Water was added into the
Beaker at room temperature (25C) and its mass and hence the volume of the. Again, crude or purified
glycerol was filled in the Beaker at same temperature and the mass of the crude glycerol was reported.
The density of the crude glycerol was obtained by taking the ratio between the mass of the sample and
the volume of the Beaker.

23
CHAPTER FIVE

5.1 CONCLUSOIN
Purified glycerol has good physical properties compared to crude glycerol because the presence of
impurities contain in crude glycerol may affect the performance of crude glycerol. Purified glycerol as a
considerable grade can be produced from the crude glycerol by-product of a transesterification reaction.
Additionally, it was found that the viscosity, pH value, moisture content, ash content. Nevertheless,
crude glycerol after purification was almost closed to physical properties values of Pure Glycerol which
show it better product of crude glycerol samples in this work. From this work, the results showed a very
efficient combination process to produce higher recovery of glycerol at high purity. Purification of crude
glycerin from its bonding to fatty acids as triglyceride in fats and oils to the market has shown the
importance of glycerin as a product that will remain strong. The nontoxic nature of glycerin and its
ability to be transformed into different other chemicals has made it a possible replacement for many
petrochemicals. The production processes from triglyceride stage to refined glycerin should be carried
out by good manufacturing practices so as to obtain better product at the end.
Impurities affect the quality of glycerin and it goes a long way to affecting the prices. To make glycerin
affordable means reducing its cost of production and it will be more profit oriented. As the drive to
reduce dependence on fossil fuel and as the quest to reduce greenhouse gases continues, there will be
the push to use biodiesel which in turn will result in production of more glycerin. Glycerin prices will
be strong despite large volume of glycerin stock because more refineries will be operating and new
applications will come on line. The biodiesel operators, on the other hand will benefit from a good
glycerin market because it will help offset the cost of production and help make biodiesel affordable.
The volatile nature of glycerin has made some investors sit on the side line. In spite of this some
companies are investing on new refineries having understood the indispensable nature of glycerin.

5.2 RECOMMENDATION

From the findings of this research it is recommended that


1. The production of high purity grade of crude glycerol is economically feasible.
2. The utilization of produced glycerol in different aspects is urgently important.
3. The presented information is devoted to open official eye on perspectives of glycerol industry.

24
4. Further studies should be developed to produce high purity glycerol in a pilot scale with meeting
the international standards.

The production of crude glycerol as a biodiesel by product has increased in a high quality and is becomi
ng a problem to bio refineries because they spend much in disposing some of this byproduct as a waste a
nd generate more revenue to the biodiesel producers. It was concluded that the purification of crude glyc
erol is feasible and cost economical as seen from the experiment conducted in the laboratory.

25
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