Malaysian Institute of Chemical and Bioengineering Technology

DESIGN PROJECT 1 (DESIGN & FEASIBILITY STUDY OF PLANT)

CPB 30703
REPORT 1

GLYCEROL PRODUCTION

Lecture’s Name: MDM FARIDAH BINTI GHAFAR.

N NAME ID SECTION
O

1 FARAH HANUM BINTI ABDUL 55213114193 L01

MU’TI

2 AINA FARZANA BINTI MOHD 55213114145 L01

SOFI

3 ALIFF FIRDAUS BIN ZAMRI 55213114127 L01

4 MOHAMMAD IQBAL BIN 55213114152 L01

NORMAN
 TABLE OF CONTENT

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1. CHAPTER 1 : SUMMARY
1
1.1 Executive Summary

2. CHAPTER 2 : INTRODUCTION
2.1 Project description
2.1.1 Introduction
2.1.2 History
2.2 Properties and Uses
2.2.1 The application of glycerol
2.2.2 Physical properties
2.2.3 Chemical properties
2.2.3.1 Oxidation of glycerol with electrolysis
2.2.3.2 Oxidation of glycerol with dichromate and
permanganate
2.2.3.3 Catalytic hydrogenation of glycerol
2.2.3.4 Oxidation of glycerol with hydrogen peroxide
2.3 Manufacturing process
2.3.1 Transesterification process
2.3.2 Saponification process
3. CHAPTER 3 : LITERATURE SURVEY
3.1 Market survey
3.1.1 Global supplier
3.1.2 Future
3.2 Production data supply
3.2.1 Prices and availability
3.2.2 Competition
3.3 Regional/ Local/ Global scenario
3.4 Literature survey
 4 CHAPTER 4 : PROCESS SELECTION
4.1 Process selection
4.2 Economy feasibility
4.3 Economy survey
4.4 Process justification
5 References

CHAPTER 1

1.0 Executive summary

Glycerol or also known as glycerine is a chemical compound with chemical

formula of C3H8O3. Glycerine was accidentally discovered in 1779 by K. W. Scheele,
the Swedish chemist, while he was heating a mixture of olive oil and litharge (lead
monoxide). Glycerol plays an important role in many industries in the world such as
pharmaceuticals, cosmetics and chemicals. The IUPAC name of glycerol is propane-
 1,2,3-triol and its molecular weight is 92.09 g/mol. It is odourless, colourless and
clear liquid with mild odour and sweet taste. Several chemical properties of glycerol
are oxidation of glycerol with electrolysis, catalytic hydrogenation of glycerol and
oxidation of glycerol with hydrogen peroxide. Basically, there are several processes
of producing glycerol, firstly is transesterification of biodiesel and second is
saponification of soap. Both of these products yields the glycerol as the by-product
with high level of purity after distillation. Transesterification is the reaction between
palm oil and methanol with the presence of sodium hydroxide (NaOH) as the catalyst
to produce biodiesel and crude glycerol. Saponification process involve the reaction
of hydrolysis between the palm oil and catalyst to produce sodium palmitate (soap)
and glycerol. Thus, we choose transesterification process to be discussed more detail
in this project.

CHAPTER 2

INTRODUCTION

2.1 Project description

2.1.1 Introduction
 Glycerol or also known as glycerine, glycyl alcohol and Propane-1,2,3-triol is a
chemical compound with formula C3H8O3. The name glycerol was derived from the
Greek word ‘glykys’ which means sweet because it has a sweet taste. Studies later
showed that the glycerol is one of the principle component of all fats and oil, in the
form of its esters called triglyceride. Glycerol was found originally for a wide variety of
uses in the production of numerous domestic, industrial and pharmaceutical products.

Glycerol is basically existing as a sweet-tasting, clear, colourless, odourless

viscous liquid. After the World War Ⅱ ended, all the commercial of glycerol was
produced as the by-product in the manufacture of soaps or from the hydrolysis of oil
and fats. Today, large amounts of synthetic glycerol are prepared from a hydrocarbon
called propylene. Crude glycerol is purified to make various grades, such as dynamite
grade, yellow distilled and chemically pure glycerol. Only the highest grades of
glycerol are used in foods and medicines.

Figure 1: Structure of glycerol

2.1.2 History

Glycerine was accidentally discovered in 1779 by K. W. Scheele, the Swedish

chemist, while he was heating a mixture of olive oil and litharge (lead monoxide).
Scheele called glycerine as the sweet principle of fat. Scheele later recognized that
other metals and glycerides produce the same chemical reaction which yields
glycerine and soap and in 1783, he published a description of his method of
preparation in Transactions of the Royal Academy of Sweden. Scheele's method was
used to produce glycerine commercially for some years. The huge potential of
glycerine went largely untapped until M. E. Chevreul, the French pioneer investigator
of fats and oils, studied it early in the 19th Century. Chevreul named Scheele's sweet
principle of fat as glycerine in 1811 after the Greek word, glykys, giving a meaning of
sweet. In 1823, Chevreul obtained the first patent for a new way to produce fatty acids
from fats treated with an alkali, which included the recovery of glycerine released
during the process. Thirteen years later, Pelouze, who is another French investigator
announced the empirical formula as C3H8O3. The accepted structural formula.
C3H5(OH)3 was established by Berthelot and Lucea almost fifty years later in 1883.
Glycerine did not become economically or industrially significant until after Alfred
Nobel invented dynamite in 1866 that is after twenty years of experimentation.
Nobel's invention successfully stabilized trinitroglycerin, a highly explosive
compound, by absorption on kieselguhr, which permitted safe handling and
transportation.

2.2 Properties and uses

2.2.1 Application of glycerol

Glycerol plays a crucial role in nearly every industry. Glycerol is used very
extensively in the pharmaceutical industry. Because of its valuable emollient and
demulcent properties, glycerol is an important ingredient in innumerable
pharmaceutical and cosmetic preparations. Glycerine is used as a solvent in the
preparation of tinctures. It is used in the preparation of elixirs, like theophylline,
 which are used to treat respiratory conditions, such as asthma and bronchitis. As a
humectant, glycerol constitutes an important pharmaceutical ingredient to prevent the
drying out of preparations, particularly ointments and creams. Since it is a sweet-
tasting liquid it is used as a sweetening agent to impart sweetness to a preparation. It
is used as a levitating agent to reduce the particle size of a drug powder. Due to its
preservative qualities, it is used as a stabilizer and an auxiliary solvent in conjunction
with water or alcohol. Glycerol is also used in the pharmaceutical industry to extract
and prevent inert materials from precipitating upon standing. It is used as a plasticizer
to enhance the spread of the coat over tablets, beads and granules. In the food
industry, glycerol is an important moistening agent for baked goods. It is also added
to candies and icings to prevent crystallization. Glycerol is used as a solvent for food
colours and carrier for extracts and flavouring agents. The smoothness of lotions,
creams and toothpaste is due to the presence of glycerol. The chemical industry uses
glycerol in the manufacture of sealing compounds and antifreeze. Glycerol is a major
starting material for nitroglycerine, also called nitroglycerol, which is used in the
manufacture of dynamites and propellants. Nitroglycerine is also an active ingredient
in pain-relieving drugs for heart patients. A large variety of mono- and diesters of
higher fatty acids are commercially manufactured from glycerine. These esters are
used as emulsifiers in foods, preparation of baked goods and modification of alkyd
resins

2.2.2 Physical Properties

Table 1.1 shows the physical properties of glycerol used in standard industrial process.

Table 1: Physical properties of glycerol

  IUPAC Name Propane-123-triol

 Another Name Glycerine, Glycyl alcohol, Propanetriol

PROPERTIES
 Molecular C3H8O
formula
 Molecular weight 92.09 g/mol
 Appearance
 Odour Colourless, odourless, clear
 Taste Mild
 Density
 Melting point Sweet
 Boiling point 1.26 g/cm3
 Viscosity 17.8 °C
 Specific gravity 290 °C
 Solubility 1.412 Pa.s
1.2636

HAZARD
 Auto-ignition 370 °C (NFPA fire protection guide to hazardous
temperature material) & 392 °C (Lewis,1997)

 Flash point 160 °C

 Flammable limit Lower : 0.9%
 Corrosive Non-corrosive
 Engineering Provide ventilation to keep the airborne
control concentration vapour below threshold limit.

 Personal protection Safety glass, lab coat, vapour respirator, gloves

Storage Keep container tightly closed. Keep container in a
cool, well-ventilated area. Hygroscopic.

2.2.3 Chemical Properties

 Below listed several chemical reactions between glycerol to produce new
products. There are a few processes, for examples are oxidation of glycerol with
electrolysis, oxidation of glycerol with dichromate and permanganate, catalytic
hydrogenation of glycerol and oxidation of glycerol with hydrogen peroxide.

2.2.3.1 Oxidation of glycerol with electrolysis

Glycerol with dilute sulphuric acid is electrolyzed between lead anode and
platinum cathode in separate chambers and the heat was avoided to give
formaldehyde, formic acid, tartaric acid, trihydroxy glutaric acid, oxygen,
carbon dioxide and carbon monoxide at the anode.

2.2.3.2 Oxidation of glycerol with dichromate and permanganate

Oxidants such as potassium permanganate, potassium or sodium dichromate

and chromic acid oxidized glycerol smoothly to CO, and H 2 in strongly acid
solution.

2.2.3.3 Catalytic hydrogenation of glycerol

Glycerol is easily reduced to propylene glycol (1,2,- dihydroxypropane) with

hydrogen at pressures from 10 to 100 atm and temperatures above 150° C.
Many catalysts may be used, e.g., Ni, Fe, Pt, Au, Hg, copper chromite or
tungstic acid.

2.2.3.4 Oxidation of glycerol with hydrogen peroxide

Glycerol oxidized by hydrogen peroxide in a strongly alkaline solution results

in the formation of formaldehyde and the production of hydrogen, but neither
is formed when the oxidation takes place in a less alkaline medium.

2.3 Manufacturing process

 Today, glycerol has become such an important chemical compound that
involve in many industries such as cosmetics, sweetening agents in food industries
and anti-freeze in chemical industries. Glycerol is mainly produce as the by-product
to several reactions such as the process of transesterification of biodiesel by using
vegetable oil and the saponification process of soap.

2.3.1 Transesterification

Basically, transesterification process involves the reaction between vegetable

oil which here in this process using palm oil, with alcohol for example methanol
with the presence of catalyst to produce biodiesel and glycerol as the by-product.
The idea of using vegetable oil as the fuel is likely from Rudolf Diesel (1858-1913)
who developed the first biofuel engine by using peanut oil. He demonstrated this
brilliant idea at the World Exhibition in Paris during 1900. During
transesterification process, the palm oil is reacted with methanol in the presence of
sodium hydroxide (NaOH) as the catalyst to initiate the process. NaOH was chosen
as the catalyst because it has lower price compared to potassium hydroxide (KOH).
It is the homogenous base catalyst that can increase the rate of reaction and the
reaction can occur at a mild condition with less energy used. On top of that NaOH
is widely available in the world including Malaysia and other South East Asia
country. This process produce the mono-alkyl ester, or biodiesel, and crude
glycerol. The glycerol produced in this process are crude glycerol which is not
purified yet. The crude glycerol is then fed into distillation column to produce the
purified glycerol that has purity of 99.33%.

Figure 1 : Chemical equation of transesterification process

 Figure 2 : PFD of transesterification process

2.3.2 Saponification of soap

Saponification is the process of hydrolysis of fat and oils (triglycerides)

with alkali resulting in two products, which are salts of fatty acid (also called soap)
and glycerol. The catalyst used in this process is zinc oxide which can help to
increase the rate of reaction. During the saponification process, the alkali break the
ester bond and releases the glycerol and soap of alkali metal. Three molecules of
soap are formed and the interaction between one molecule of triglyceride and three
molecules of alkali liberates one molecule of glycerol. Caustic alkali react
spontaneously with free fatty acid and soap is formed immediately under the
condition of adequate mixing and agitation. The soap is filtered and the filtrate
contains 35% glycerol, free alkali, soluble soap, some sodium chloride, NaCl as
well as suspended impurities. This saponification reaction forms the foundation of
the soap making industry and is the basis of the commercial soap-making process.
The process of soap manufacture of fat and oils usually yields glycerol to about
10% of the value of the soap formed.

Figure 3 : Chemical equation of saponification process

Figure 4 : P&ID of saponification process.

 CHAPTER 3

LITERATURE REVIEW
3.1 Market survey

3.1.1 Global supplier

Soon nations with extensive accessibility of land, for example, Argentina and
Brazil on the other hand, where palm or coconut oil manors were set up, for example,
Malaysia, the
Philippines, Indonesia, Colombia and Thailand began to make and offer
vegetable oils to biodiesel producers in Europe and in the US, and to and
oleochemicals makers in Asia.
The result was a surge of glycerol that disturbed a synthetic market that in the
previously mentioned petrochemical split existed since the mid-1940s even
in spite of the fact that generation of cleanser determined glycerol or glycerol began
as ahead of schedule as the late 1850s with the commercialization of the principal
individual care purchaser items in Europe and in the US.
 In 2005 the top three global glycerol suppliers were Procter & Gamble, Cognis
and Uniqema (now Croda) that combined had more than one third of the market
share.

Five years later, the main glycerol suppliers had become biodiesel and
oleochemical companies mostly based in the Asia Pacific region (Malaysia, India,
Indonesia and Philippines, Table 1).
 To ingest this excess, growing new concoction employments of glycerol as
stage synthetic
A1bruptly got to be urgent.12 The quantity of research papers managing new uses for
glycerol distributed yearly somewhere around 2000 and 2007 multiplied to more than
7000, and a number of new reactant courses to high included esteem items were found
or rediscovered, enhanced and connected, for example, on account of the acidic
corrosive catalysed course
to epichlorohydrin now effectively created by Solvay and by a few other compounds
organizations in Asia and in Europe.

3.1.2 Future

There are few end uses that need large amounts of glycerol in their formula.
Uses vary from energy bars to cough syrups to sealants for ships. The three main uses
for refined glycerol are food products, personal hygiene products and oral hygiene
products, making up about 64% of total consumption. For a long time, consumption
of oil and fat was divided among food, animal feed, and industrial use at 80:6:14
ratio, but with the increase in biodiesel production this is probably closer to 74:6:20
now and is expected to reach 68:6:26 in 2020, showing that industrial usage has been
growing in recent years.
 Pyrolysis and gasification of glycerol were also found by many researchers to
generate CO, H2. Glycerol is a readily digestible substance that can be easily stored
for a long time. The relatively high energy content in the glycerol phase also makes it
an interesting substrate for catalytic reforming resulting in hydrogen and carbon
monoxide, called syngas, by steam reforming in smaller reactor volumes and
production of H2 by reforming glycerol. Is used in production of fuel oxygenate acetal
(2,2-dimethyl-1,3-dioxolan-4-yl). Selective glycerol trans esterification and
esterification can yield monoglycerides (MG) and polyglycerol esters (PEG). MG can
be applied as emulsifiers in the food, pharmaceutical, and cosmetic industries. Melero
et al reported the esterification of glycerol with acetic acid to produce glycerol
acetates, such as diacetylglycerol (DAG) and triacylglycerol (TAG), which have been
shown to be valuable petrol fuel additives leading to either enhanced cold and
viscosity properties when blended with diesel fuel or anti-knocking properties when
added to gasoline. A glycerol-based fuel additive, glycerol tertiary butyl ether is an
excellent additive and there is a lot of potential for diesel to be synthesized via
etherification of glycerol. Selective etherification of glycerol can yield more valuable
fuel additives or solvents with suitable properties. Among these, tertbutyl ethers
exhibit potential for use as diesel fuel additives in gasoline. They offer an alternative
to oxygenates such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether
(ETBE). Selective etherification can also convert glycerol into polyglycerol (PG) and
PEG, which have been recommended to be used as biodegradable surfactants,
lubricants, cosmetics, food additives. Carboxylation of glycerol can produce glycerol
carbonate.
A lot of attentions have been given to this new and interesting material in the
chemical industry. Inexpensive glycerol carbonate can be utilized as source of new
polymeric materials. New applications have been found in the polyglycerol,
polycarbonate and polyurethane industry in the field of stabilizing wood and
production of small molecules such as glyceric acid, hydroxipyruvic acid and glycerol
carbonate. Recently, the production of 1,3- propanodiol (1,3-PD) or trimethylene
glycol (TMG) is gaining increasing importance due to its role as a monomer in
polyester synthesis processes for tissues and textile applications, which require a large
increase in the production of this product. Glycerol can also be used to prepare
dichloropropanol (DCP) and as substrate to produce organic solvent tolerant lipase.
Polypropylene can be made from glycerol. This plastic is used in vehicles, appliances,
 disposable syringes, cleaning products, and others. In biological conversion, many
known microorganisms can naturally utilize glycerol as their only source of energy
and carbon utilized in biological methane production from crude glycerol by
anaerobic digestion. The higher level of sugar reduction allows reduced chemical
products to be obtained, such as succinate, ethanol, xylitol, propionate, and hydrogen
at higher yields than those obtained using sugar.

3.2 Production data supply

3.2.1 Prices and Availability

For a considerable length of time the glycerol market was for the most part
dedicated to direct use with just two real synthetic end-utilizes as crude material,
specifically in the fabricate of nitroglycerine also, in alkyd gums generation.
Profoundly unadulterated glycerol was sold at high cost (2500-4000 $/t) to
pharmaceutical and individual care item producers and, before the biodiesel blast, the
related incomes were a critical part of the gainfulness of the cleanser and
oleochemicals businesses. Since 2003, in any case, the quickly expanding glycerol
over supply brought about an emotional fall in the cost of both refined and rough
glycerol.
 Figure 4

In detail, the cost for refined glycerol (99.5% genuine review) diminished
from about 4000 €/t in year 2000 to not exactly € 450/t in mid-2010, when the cost of
rough glycerol went to € 0 for each ton, i.e. bioglycerol had turned into a waste result
of no financial esteem, whose exclusive utilize was as low-vitality content fuel for
burning or for steers sustaining.

Then again, such exceptional low costs produced new request in China, India,
Russia and Latin America, specifically vast locales of the world where glycerol in
different ranges, for example, oral and individual care, pharmaceuticals, and
sustenance and drink items was generally not utilized because of its high cost. The
quickly rising expectations for everyday comforts of purchasers in these expansive
nations met the offer of minimal effort of glycerol. Subsequently, for instance, in
2010 the primary shopper of EU glycerol was Russia, retaining 30% of the aggregate
Europe's fare conveyances.

In prosperous economies, as well, glycerol utilization climbed significantly (in

the EU in 2010 it expanded in one year just by 21%, to 319,698 tons). Comparative
twofold digit development was recorded in the Unified States and in South East
("Asia-Pacific").The last locale outperformed Europe as the biggest market in 2009.
Today, Asia-Pacific speaks to the biggest and in addition quickest developing
provincial market for glycerol worldwide with expanded interest for all applications,
including new markets for refined glycerol, for example, creation of epichlorohydrin.
Concomitantly, in reality, new modern procedures for the generation of
epichlorohydrin propylene glycol, that require refined (and not rough) glycerol, were
set up in China, Thailand and, to a lesser degree, in Europe and in the US.

Minimal effort glycerol is utilized as low - glycemic sweetener and is

supplanting already less expensive polyols in numerous applications. For instance,
today glycerol is less costly than different humectants, for example, propylene glycol
and sorbitol. Subsequently, glycerol has turned into a vital segment for grain makers
and dried natural product processors because of its capacity to upgrade timeframe of
realistic usability of items (glycerol averts dampness misfortune as well as jelly the
surface of sustenance items, building humectancy of oats, raisins and dried organic
products).

On account of the blend of new applications, advertise extension in

conventional markets and substitution of different polyols, the cost of glycerol
halfway recouped since the 2009 memorable lows. As of mid-2014, in the US
pharmaceutical review glycerol could be purchased for $900 per ton, while unrefined
glycerol (80% immaculate) was sold at 240$/tonne.24 Yet costs never achieved the
abnormal states expected by numerous experts.

Showing the price trend for refined glycerol up to 2003, Figure 5 contains the
prediction of a researcher that by 2010 the glycerol price could be “as low as $0.35
per lb. Subsequent developments have shown that the above prediction was too
conservative. The refined glycerol price plunged even more rapidly. In early 2007 it
was29-35cents/lb.; while at the end of 2009 prices were in “the low -to-mid 30s”.In
early 2012, the price started to recover with prices of vegetable glycerol in the US
recorded at $838/tonne-1,014/tonne,28 and at $700-780/ton in Asia;29 with good
global demand across several key end-uses, particularly in food-grade and
pharmaceutical applications. Eventually, in late 2013 (tallow) glycerol contract prices
in the US were around $900/tonne;30 and Asia’s (vegetable) refined glycerol prices
were reported at an average of $965/tonne due to higher feedstock (vegetable oil)
prices.
3.2.2 Competition

Biorefineries depend on the combination of the biomass transformation

procedures to create power, fills and chemicals. In this specific situation, the use of
glycerol created in the biodiesel generation handle offers a fantastic chance to get
chemicals by microbial maturation. Creation yields of powers and chemicals from
glycerol as high as 90% of hypothetical most extreme have been acquired. These high
generation yields of the sought item ought to make the foundation of bioprocesses
simpler. Regardless of the possibility that the accessible delivering strains have not
been assessed at pilot scale yet, advertise interest for green chemicals, new
procedures, and advances for lignocellulose biorefineries ought to encourage the
improvement of mechanical procedures in light of unrefined glycerol.

A limitless scope of energizes and chemicals can possibly be created by

microbial maturation of glycerol. In any case, the desire is that the essential items
acquired by aging in biorefineries are chemicals with built up requests and worldwide
markets. Actually, from the fourteen mixes created at lab scale by microbial aging of
glycerol, ten of them are these days delivered by compound or microbial
transformation of sugars or petrochemical forms. Additional fascinating, these
chemicals are vital stage chemicals or items that have a merged market request of a
huge number of tons every year. In this manner, once a creation procedure in view of
glycerol aging for any of these chemicals is produced, the item could without much of
a stretch enter the market. Then again, it is imperative that creation expenses of
chemicals from glycerol stay aggressive with those acquired from petroleum. It ought
to be noticed that requests for maintainable advancement and unpredictable petroleum
costs ought to support the utilization of "greener" chemicals in the long haul,
regardless of the possibility that their market cost is not significantly less expensive.
Chemicals without or with a restricted market, as DHA and glyceric corrosive, may
speak to an open door for the advancement of new items as there is no immediate
benchmark generation value they should go up against.

Control of organisms to permit the cost focused business generation of energizes and
chemicals, for example, ethanol, butanol, isoprenoids and others, on sugar and
lignocellulose has progressed essentially in the most recent years. To be sure, a few
procedures in light of built microorganisms, particularly yeast and microscopic
organism species, have been created and actualized. Two cases of progress are given
by the generation of 1,3-PDO and succinic corrosive. The concoction 1, 3-PDO is
customarily produced using fossil-inferred ethylene oxide or propylene, nonetheless, a
bio-based process has been created and actualized by DuPont and Tate and Lyle.
Their procedure for creation of 1,3-PDO depends on an organism communicating
qualities from a few distinct microorganisms to give the required profitability. The
procedure in light of the utilization of an architect microorganism to deliver 1,3-PDO
from corn has been running in a Bio-PDM plant in Tennessee (USA) with a limit of
45 thousand tons a year since 2007. Comparative methodologies are being created for
succinic corrosive. Bio-based succinic corrosive generation by a fermentative
innovation is the centre of a joint wander amongst DSM and Roquette. Without a
doubt, the primary testing volumes of this renewable and adaptable compound
delivered from corn have as of now been created in an exhibition plant in Lestrem
(France) that was implicit 2009. These advancements are relied upon to encourage the
foundation of glycerol-based maturation forms, since comparative microorganisms
and pathways might be utilized.

In spite of the fact that the difficulties of getting microbial strains ready to
work under mechanical process conditions have been defeat, another test for the
generation of powers and chemicals from biodiesel industry rough glycerol is the
production network. From the financial perspective, it is imperative for the business
that the feedstocks for biodiesel creation, and thusly glycerol for powers and
chemicals generation, are bottomless year around. In this sense, a few nations might
not have adequate biomass, and therefore glycerol, to keep up a modern scale
generation of biodiesel, fills and chemicals all through the four seasons, particularly
because of rivalry of biomass for different employments. One approach to tackle this
issue, particularly in nations with endless region and mellow atmosphere year round,
is the broadening of biomass feedstocks in the business and regionalization of creation
plants. In this sense, the primary feedstock for the business ought to develop in the
locale of the generation plant, which may just be supplemented by option biomass
from different districts. In nations like Brazil, for instance, where 80% of biodiesel is
created from soybean oil, it may be worthwhile to begin utilizing oil from option
 biomass sources, similar to palm oil, physic nut, castor bean and others. This would
ensure the supply of biomass for the business and in the meantime, stay away from
transportation of soybean to creation plants around the nation.

3.3.3 Regional/ Local/ Global scenario

As biodiesel creation, has expanded, glycerol generation has developed and

soaked the market. In 2005, world glycerol request was evaluated at 900 thousand
tons. For 2007, Asia was the biggest shopper of refined glycerol with 25% of
consumption. Western Europe was the second biggest refined glycerol purchaser, with
28% of world utilization in 2007. North America was the third biggest buyer. These
three locales represented 82% of world utilization in 2007. Generally, Europe imports
refined and rough glycerol from Asian nations. It is viewed as a commonplace shipper
of this resource. The United States is likewise a glycerol merchant, accepting item
from Indonesia, Malaysia, Argentina, and Europe.

Asia trades on a vast scale to worldwide and provincial markets, and glycerol
is a nearby final result. As of late China has surged in the market as an expansive
shipper, notwithstanding having nearby creation. What's more, because of the
developing petroleum and synthetic ventures in Asia, a significant part of the glycerol
generation had before been traded to the United States, however with developing
cargo costs, a large portion of this creation wound up going to China. The Asia-
Pacific locale surpassed Europe as the biggest showcase in 2009 and is currently the
biggest local market with the speediest development on the planet, pushed by the
expansion in glycerol applications in different segments, for example, pharmaceutical,
individual cleanliness, sustenance and drink items. There are lower importation rates
in some Asian markets. This market had anticipated yearly development of around
3.3% every year from 2007 to 2015. New refined glycerol markets are likewise to a
great extent in charge of anticipated development of world request from 2007 to 2012,
and for 2012 Asia is still anticipated that would be the biggest market because of
expanded interest for some applications including new markets for refined glycerol.
 The overall glycerol market is known for its erratic and complex nature, since
it is a repercussion. Generation of the compound is specifically influenced by the
request by different end-utilize portions. Interest for glycerol dove from 2008 through
2009 in light of a drop in the large-scale economy. The negative effect of the retreat
was obviously apparent in numerous locales. In any case, the glycerol market is relied
upon to recuperate by 2011/2012 and manage development in the resulting years.
Likewise, utilization of glycerol in different new applications is required to enhance
glycerol request in the close term. Be that as it may, the glycerol showcase recouped
in 2012 and manages development for the next years. It is normal that by 2016, China
will represent 27% of the world's refined glycerol utilization. Thailand will likewise
encounter high development rates as a consequence of epichlorohydrin generation.
Both Indonesia and Malaysia will keep on send out a lot of refined glycerol. Japan's
refined glycerol utilization development is required to stay level in the following quite
a long while. Generally speaking, Asian utilization will altogether increment to 45%
of the worldwide refined glycerol adds up to in 2016.

3.4 Literature survey

3.4.1General information

Biodiesel is a promising alternative, and renewable, fuel. As its production

increases, so does production of the principle co-product, crude glycerol. The
effective utilization of crude glycerol will contribute to the viability of biodiesel. In
this review, composition and quality factors of crude glycerol are discussed. The
value-added utilization opportunities of crude glycerol are reviewed. The majority of
crude glycerol is used as feedstock for production of other value-added chemicals,
followed by animal feeds.

3.4.2 Uses of glycerol

Around the world, glycerol got from biodiesel change has expanded from 200,
000 tons in 2004 to 1.224 million tons in 2008. In the interim, the worldwide market
for refined glycerol was assessed to be approximately 900, 000 tons in 2005.
Subsequently, it is of extraordinary significance for researchers to discover new
applications for refined and glycerol. As of late, various papers have been distributed
on direct usage of glycerol from biodiesel generation. In the accompanying areas,
point by point talks on use of glycerol are introduced.

3.4.3 Uses in Animal feedstuff

Utilizing glycerol as a bolster element for creatures goes back to the 1970s.
Be that as it may, glycerol's use in sustains has been constrained by the accessibility
of glycerol. As of late, the conceivable outcomes of utilizing rough glycerol from
biodiesel as a part of encourages have been researched in light of the expansion in the
cost of corn and the excess of unrefined glycerol.

3.4.3.1Glycerol in non-ruminant diets

Glycerol has high ingestion rates and is great vitality source. Once
ingested, it can be changed over to glucose for vitality generation in the liver
of creatures by the chemical glycerol kinase. Glycerol tests, from various
biodiesel makers, were examined as vitality sources. The edible vitality (DE)
values for 85% of the glycerol tests were in the scope of 14.9-15.3 MJ/kg with
metabolizable vitality (ME) values in the scope of 13.9-14.7 MJ/kg. Glycerol
was a magnificent wellspring of calories for non-ruminants, for instance, the
ME decided in grills, laying hens and swine were 15.2, 15.9 and 13.4 MJ
ME/kg, individually. In developing pigs and laying hens, 14.0 MJ/kg evident
DE and 15.9 MJ/kg nitrogen-redressed obvious ME (So be it) were accounted
for, individually, which inferred that unrefined glycerol was utilized
proficiently. The so be it of glycerol was metabolized proficiently by grill
chickens with a so be it of 14.4 MJ/kg. That was fundamentally the same as
the general vitality (GE) of 15.2 MJ/kg. In nursery pigs, the GE grouping of
glycerol relied on upon the convergence of glycerol, methanol, and
unsaturated fats, with ME as a percent of GE averaging 85.4%.

In spite of the fact that glycerol can be added to creature nourish,

abundance glycerol in the creature eating regimen may influence ordinary
physiological digestion system. A couple of original copies have been
distributed that centred on the levels of glycerol bolstered and the execution of
glycerol in creature encourages. The change of day by day picks up by pigs
relied on upon the genuine admission of glycerol amid the developing time
frame however not on the completing time frame. The dietary medications had
no huge consequences for meat quality. At the point when glycerol was added
to the eating methodologies of weaned pigs, at levels up to 10%, the sustain
execution was improved. Up to 9% glycerol could be added to the eating
regimens of lactating sows with exhibitions like sows bolstered standard corn-
soybean dinner control diets. No unfavourable impacts, as for egg execution,
egg quality, supplement maintenance, and metabolizable vitality, were found
when glycerol was fused at a level of 6% in the eating routine of laying hens.
In grill diets, expanding the admission level of glycerol expanded bolster
change proportion however did not influence development execution and
supplement absorbability. Glycerol was utilized viably at levels of 2.5 or 5%.
Be that as it may, the utilization of 10% rough glycerol brought about poor
encourage stream. The impacts of levels and nature of glycerol on pellet
quality needs advance study.

3.4.3.2 Glycerol in ruminant diets

Glycerol, added at up to 15% dry matter in the weight control plans of

completing sheep, could enhance feedlot execution, particularly amid
the initial 14 d, and had no related impact on body qualities. Contrasted
with mid-range quality feed, diets for meat goats with up to 5% rough
glycerol ended up being helpful. What's more, the consideration of
cleansed glycerol at up to 15% of the dry matter proportion of lactating
dairy cows was conceivable, without injurious consequences for
nourish consumption, drain creation, and yield. At the point when
glycerol was included at levels of 8% or less, in light of dry matter in
dairy cattle completing eating methodologies, it enhanced weight pick
up and bolster effectiveness. Aside from the previously
mentionedexaminations, a patent depicted methodologies for utilizing
 or fusing glycerol into creature nourishes and also encouraging
suggestions.

On the whole, the utilization of glycerol as a creature

encourage part has extraordinary potential for supplanting corn in
eating methodologies, and is increasing expanding consideration. In
any case, one must know about the nearness of potential dangerous
contaminations in unrefined glycerol from biodiesel. For instance,
leftover levels of potassium may bring about wet litter or lopsided
characteristics in dietary electrolyte adjust in grills. The levels of
methanol must be minimized on account of its poisonous quality. More
consideration ought to be paid to the glycerol from little scale biodiesel
offices that utilization straightforward cluster refining or vanishing
methods.

3.4.4 Uses for chemicals via Biological Conversion

3.4.4.1 1, 3-propanediol

The anaerobic fermentative generation 1, 3-propanediol is the most

encouraging alternative for natural change of glycerol. Muel exhibited that rough
glycerol could be utilized specifically for the generation of 1, 3-propanediol in
sustained bunch societies of Klebsiella pneumoniae. The contrasts between the last 1,
3-propanediol focuses were little for rough glycerol from the methanolysis of soybean
oil by soluble base (51.3 g/L) and lipase-catalysis (53 g/L). This suggested the
organization of glycerol had little impact on the natural transformation and a low
aging expense could be normal. Assist, the creation of 1,3-propanediol by
K.pneumoniae was streamlined utilizing reaction surface system. The greatest yield of
1, 3-propanediol was 13.8 g/L. All the more as of late, the generation of 1, 3-
propanediol, from glycerol from Jatropha biodiesel by K.pneumoniae ATCC 15380,
was streamlined. The acquired 1, 3-propanediol yield, immaculateness and
recuperation were 56 g/L, 99.7% and 34%, individually. Moreover, a fused bioprocess
that consolidated biodiesel generation by lipase with microbial creation of 1, 3-
propanediol by K.pneumoniae was produced in an empty fiber film. The bioprocess
kept away from glycerol hindrance on lipase and diminished the creation cost.

Clostridium butyricum additionally could be utilized to create 1, 3-propanediol

from glycerol. For instance, C. butyricum VPI 3266 could create 1, 3-propanediol
from glycerol on a manufactured medium. Minor contrasts were found between
business glycerol and glycerol. C.butyricum strain F2b and C.butyricum VPI 1718
possibly could change over glycerol to 1, 3-propanediol. Keeping in mind the end
goal to maintain a strategic distance from the detachment of 1,3-propanediol from
glycerol aging media, a one vessel bio-and chemo-reactant process was created to
change over glycerol to auxiliary amines straightforwardly in a biphasic framework
without middle of the road partition of 1, 3-propanediol. Furthermore, Chatzifragkou
considered the impacts of various polluting influences in glycerol on 1, 3-propanediol
creation by C.butyricum. The twofold bond from long-chain unsaturated fats or
methyl esters may impact the development execution of the microorganism, methanol
did not influence the microbial change and the nearness of NaCl had certain impact
amid a consistent procedure however not a clump procedure.

3.4.4.2 Citric acid

A couple reports are accessible on the utilization of glycerol for citrus extract
biosynthesis. The generation of citrus extract from glycerol by Yarrowia lipolytica
ACA-DC 50109 was not just like that acquired from sugar-based customary media
additionally single-cell oil and citrus extract were delivered all the while. At the point
when encouraged cluster maturation by acetic acid derivation negative mutants of Y.
lipolytica Wratislavia AWG7 strain was utilized to age glycerol, the last centralization
of citrus extract was 131.5 g/L, like that acquired from immaculate glycerol (139 g/L).
Then again, when Y.lipolytica Wratislavia K1 was utilized, a lower convergence of
citrus extract (around 87-89 g/L) and a high centralization of erythritol (up to 47 g/L)
were gotten. It was in accordance with the outcomes appeared by Rymowicz.
Encourage, Y. lipolytica Wratislavia K1 turned out to be better than different strains
by creating erythritol and not citrus extract from glycerol under ideal change
conditions, which might be a profitable advancement. Y.lipolytica LGAM S (7)1
likewise demonstrated potential for changing over glycerol to citrus extract.

3.4.4.3 Docosahexaenoic acid

A progression of papers on the generation of docosahexaenoic corrosive

(DHA)- rich green growth were distributed, utilizing glycerol, by aging of the alga
Schizochytrium limacine. For supporting alga development and DHA creation, 75-
100 g/L centralization of glycerol was suggested as the ideal range. The algal DHA
yield was affected fundamentally by temperature and ammonium acetic acid
derivation focus. The ideal sums for temperature and ammonium acetic acid
derivation were 19.2°C and 1.0 g/L, separately. The most astounding DHA yield
acquired was 4.91 g/L under the enhanced culture conditions. Distinctive wellsprings
of glycerol did not bring about critical varieties in algal biomass structures. The
subsequent green growth had a comparable substance of DHA and a similar nutritious
profile to business algal biomass. That proposed great potential for utilizing glycerol-
determined green growth as a part of omega-3-sustained nourishments or bolsters.
Advance, DHA-containing green growth has been created as trades for fish oil for
omega-3 unsaturated fats. Rough glycerol was utilized to deliver parasitic biomass
that served as eicosapentaenoic corrosive (EPA)- strengthened sustenance or
encourages through contagious aging with organism Pythium irregular. Developing in
medium containing 30 g/L glycerol and 1.0 g/L yeast remove, the EPA yield and
profitability could achieve 90 mg/L and 14.9 mg/L every day, individually. The
subsequent EPA substance was low contrasted with microalgae for EPA. Advancing
society conditions and growing high cell thickness culture methods are basic in future
work. As of late, it was accounted for that consistent culture was a compelling
methodology for examining the development energy and practices of the green
growth on glycerol.

3.4.4.4 Lipids
 As the sole carbon source, glycerol could be utilized to create lipids which
may be a practical biodiesel feedstock. For instance, glycerol could be utilized for
refined Schizochytrium limacine SR21 and Cryptococcus curvatus. S. limacine algal
development and lipid generation were influenced by the convergences of glycerol.
Higher convergences of glycerol effects affected cell development. For clump refined
of unrefined glycerol got from yellow oil, the ideal glycerol focuses for untreated and
treated glycerol were 25 and 35 g/L, individually. With 35 g/L, the acquired most
noteworthy cell lipid substance was 73.3%. Methanol staying in glycerol could hurt S.
limacine SR21 development. For C. curvatus yeast, encouraged cluster was a superior
procedure than bunch for lipid generation. Refined for 12 days, the lipid content from
one-arrange encouraged clump operation and two-organize sustained cluster process
were 44.2% and 52%, separately. Methanol did not have huge inhibitory impact on
cell development. The created lipid had high convergence of monounsaturated
unsaturated fat and was great biodiesel feedstock.

Advance, Saenge displayed that oleaginous red yeast Rhodotorula glutinis

TISTR 5159, refined on glycerol, delivered lipids and carotenoids. The expansion of
ammonium sulfate and Tween 20 expanded the aggregation of lipids and carotenoids.
At the point when encouraged clump aging was utilized, the most astounding lipid
content, lipid yield and carotenoids creation were 10.05 g/L, 60.7% and 6.10 g/L,
individually. Chlorella protothecoides likewise unrefined glycerol to lipids. The lipids
yield was 0.31 g lipids/g substrate. Likewise, with C. protothecoides and glycerol
(62% immaculateness), Chen and Walker exhibited that the most extreme lipid
efficiency of 3 g/L every day was acquired in a bolstered clump operation, which was
higher than that created by group prepare. Also, Chatzifragkou concentrated on the
capability of fifteen eukaryotic microorganisms to change over glycerol to metabolic
items. The outcomes demonstrated that yeast amassed restricted lipids (up to 22 wt.%,
wt/wt, on account of Rhodotorula sp.), while organisms aggregated higher measures
of lipids in their mycelia (going somewhere around 18.1 and 42.6%, wt/wt, of dry
biomass).

3.4.4.5 Other uses

 Past the previously mentioned utilizes, a couple of other potential uses of
glycerol have been accounted for. Glycerol was utilized as a high-breaking point
natural dissolvable to upgrade enzymatic hydrolysis of lignocellulosic biomass.
Unrefined glycerol (with no cleansing) additionally could be utilized as a green
dissolvable for natural responses. Two delegate responses were base catalyzed also
buildup and palladium catalyzed Hell carbon-carbon coupling. Working as a natural
carbon hotspot for the expulsion of nitrate in the wastewater denitrification handle,
the denitrification productivity could be expanded by 2.0-5.0 mg NO3-N L-1 for each
unrefined glycerol measurements of 100 L . Moreover, glycerol could be utilized as a
fuel for producing power from microbial energy components. Both co-aqueous
pyrolysis and co-liquefaction of fertilizer with glycerol could enhance the generation
yield of bio-oil. Be that as it may, for the co-liquefaction, an excessive amount of
expansion of glycerol influenced the carbon substance and warmth estimation of the
bio-oil.

3.4.5 Regulation of biodiesel production

For the regulation of biodiesel production, Defra has received question about
the production is regulated under PPC (EP Regulation).On top of that, there are some
advice from the Environment Agency .Firstly, biodiesel can be produce by chemical
or physical production routes using either waste or virgin oil. Trans-esterification is
use to process chemical production with several methods. The method are heat the oil,
filter methanol or ethanol that added, together with a small amount of sodium
hydroxide catalyst. After that, the mixture separates in a settling tank and the by
product which is glycerol is removed. Besides that, physical production involves the
physical blending of ingredients which is happen in typical process when oil is heat to
melt the fat and remove water. Next, the filter and blended process with hydrocarbon
was proceeded to modify the cetane rating. Using the trans-esterification process
,biodiesel is produced for commercial purpose which is chemical activity regulated
under Section 4.1 of the Environmental Permitting Regulation 2007.The glycerol as
the by product should be sent to another operator for beneficial use, but where this is
not possible it must be consigned as waste to an appropriately licensed or permitted
waste facility. The risk of very small-scale commercial production is less than 5000
liters per year which is low and for this reason is not usually subject to the
requirement of the Environmental Permitting Regulations. If biodiesel is being
produced by the trans-esterification process for personal use, do not regulate this as it
is not considered to be commercial production. This also applies to collective small-
scale production by a group of individuals if it is just for their own use. The group
also should be a properly constituted community group, with members participating
on a not-for-profit basis.

3.4.6 Conclusion
The glycerol's cost is verifiably unstable. Preceding the biodiesel blast, when
one fourth of the worldwide and generally low request was met by manufactured
glycerol and the rest from cleanser and oleochemicals fabricating, the cost was
managed essentially by climate and by the fluctuating interest of cleanser and greasy
alcohols. This unpredictability, that once was connected to the unpredictable request
of a concoction fundamentally utilized by the pharmaceutical what's more, individual
care enterprises, today starts from the unpredictable way of the glycerol supply which
in its turn is affected by two principle components legislative issues and oil. As it
were, as glycerol today starts as a by-product of biodiesel and unsaturated fats and
greasy alcohols fabricating, its supply is altogether free of market request. There is as
much glycerol as much vegetable oils are changed over into biofuels, furthermore,
oleochemicals. Said something else, this is one of only a handful couple of cases in
financial aspects of a great whose cost is not influenced by the interest for different
end-utilize fragments.
 CHAPTER 4

PROCESS SELECTION

4.1 Process comparison

4.1.1 Transesterification process
There are certain type of process that can produce a glycerol. There are three
process that have potential of glycerol’s source that is transesterification, based-
catalyst, acid-catalyst, and enzymatic-catalyst, saponification and hydrolysis. Glycerol
can be produce from the triglycerides (fats and oils) transesterification as by-product
in biodiesel production. Theoretically, the transesterification is the process whereby
the alcohol such methanol react with fats and oils (triglycerides) by addition of
catalyst to produce biodiesel (methyl esters) and the glycerol which is by-product.
There are two type of reactors as well as batch reactor and continuous stirred tank
reactor (CSTR). Because of these two componenst have different density and the
polarities. This process on the reaction stream, there are two separates phases,
biodiesel- rich phase (top layer) and glycerol rich phase (bottom layer) .

Based on ( Tan H.W et al, 2013) , the production of 100 kg of biodiesel yields
will produce about 10 kg of crude glycerol, with purity of 50-55%. From the
transesterification process, the crude glycerol has impurities of excess alcohol and
higher salt content. For the biodiesel production, the major process was applied is
transesterification. (H.W. Tan et al, 2013) was reported that due to the drastic
production of glycerol, it causes the excessive of glycerol stock in industrial which
lead to consequence of decreasing of glycerol’s price. Besides the reporter also stated
the impurities of glycerol surplus will gave a bad impact to the public and
environment policy.

Biodiesel industry which from the process of transesterification of

triglycerides (fats and oils), (CH2COOR)3 which react with methanol (3CH3OH) .
From the research of (Ahmad et al, 2011), he found that about 75% of biodiesel
production cost are the price of the feedstock which is a high value cost of the raw
material used. Hence to minimize the capital cost there must be a proper way to select
the more suite of raw material applied which low cost as well as give maximum of
product will formed. Since the source of fats and oils are varies, they will categorized
into three group of biodiesel feed stock. First generation of feedstock in biodiesel
production is palm oil, sunflower oil, soybean oil, rapeseed and peanut oil. They are
food feedstock they are limited and will have composition with other edible oil in
market. The second generation is tallow, jatropha oil, sea mango and waste cooking
oil. The second generation of feedstock were reduced competition of feedstock and
due to the small crop in farmland will provide environmental friendly. Microalgae is
the third generation. Since it is easy to cultivate it will rapid the reproduction stage.

Many researcher have conduct the biodiesel production in order to identify the
yield of glycerol produced by using different source of feedstock and operational
condition such temperature, pressure also the feedstock composition. Biodiesel will
produce from the transesterification reaction by introduced waste cooking oil and
animal fat as reported by Enamul Hoque. He was conducted this process at optimum
condition by 6:1 ratio of methanol to oil. The concentration of catalyst is 1.25% of oil,
65°C of reaction temperature and 1 atm of pressure. By using of waste cooking oil,
the author determined that the maximum biodiesel production is about 87%. Certain
developer was use biological technology means they was use miroalgae as a raw
material and H2SO4 as a catalyst through this process.

There are two ways of transesterification process that distinguish by the

category of catalyst use which are acid or based. This process will undergo either
homogenous or heterogenous system. For acid catalysed transesterification the most
suitable mixture in heterogenous but base catalysed were suite with homogenous
solution. The waste cooking oil are often partner with acid-catalyst in the reaction.
The feasibility study must be done in order to select the best reaction to optimize the
reaction. The study are more focus on homogenous base catalyst and heterogenous
acid catalyst. For homogenous base catalyst transesterification, the catalyst to be used
is NaOH and KOH. The rate of reaction was fast and the reaction apply the low of
utilizing of energy. It also produced high conversion of desired product. The type
catalyst apply has a wide range and economical. It also has a huge range of uses.
There are several weaknesses of this reaction which the type of oil used must not
more than 0.5%. For heterogenous acid-catalysed, the catalyst type is ZRO2 and
TiO2. When the oil has content with FFA and water there are usually negligible.
Besides, this method are usually apply by using waste cooking oil but it is higher cost
process. It applys big values of temperature in system. In order to achieve the
objective such to minimize the cost production, maximize the product and reduced the
energy utillization , hence the best of process selection is homogenous base catalysed.
Concrete reason in select this process is the reaction take place are fast. In addition, it
will produce high conversion of biodiesel and glycerol.

Figure

Fig. 2 shows the (process flow diagram) PFD of a conventional

biodiesel plant with retrofitted distillation columns. The biodiesel plant uses
methanol , palm oil, NaOH as the basic feed streams, and produce fatty acid
methyl ester (FAME) about 98% and 99.36% of pure glycerol and 90.18% of
pure water. Mixer M102 will mixed recycle and fresh methanol and oil before
sending to the Continuous Stirred Tank Reactor (CSTR) reactor, R101, as
shown in Fig. 2. In CSTR reactor the FAME will be generate by catalyzed of
NaOH in transesterification process at 60°C and glycerol as by product. The
methanol/oil molar ratio is 6:1and 95% percent oil conversion was assumed.
The reactor outlet contains FAME, methanol, oil, water, NaOH, and glycerol
is pumped into the extractor EX101 and to partially extract polar components
from the mixture it was uses water as a solvent. At the distillation column
 T101 the distillate product is fed to at stage 2 where the FAME is purified.
There is four stages of this column operates with a kettle reboiler partial-
vapor-liquid condenser. FAME are obtain at bottom product containing some
and mostly oil is recycled to the reactor. The vapor phase stream containing
small amounts of water/methanol is a waste stream while the distillate is the
product FAME.

Phosphoric acid (H3PO4) are fed to the reactor R102 where acid/base
neutralization reaction takes place at the bottom flow of the extractor EX101
and the liquid water, methanol, glycerol, and some solid Na 3PO4 are formed
at the reactor outlet. The solid waste is separates by Separator SEP101 while
the flash drum F101 liquid will receive stream S8 to where the separation of
glycerol from methanol and water takes place. Pure glycerol are obtain at the
bottom product while the distillate is cooled to 80°C and fed to stage 9 of
distillation column T102 for purification of methanol. Column T102 has total
condenser and a kettle reboiler also most important things it has 12 stages. The
bottom product is mainly water and through mixer M101 the distillate
methanol is recycled. In order to estimate the vapor properties in column
T101 the thermodynamic model of UNIFDMD was used, while the activity
coefficient model NRTL model is used for evaluating the equilibrium and
liquid characteristic in column T102 as reported by (Nguyen T.N, 2012). The
reporter also found that both the thermodynamic models are listed within the
Aspen Plus and are chosen based on the type of the feed mixture and non-
ideality in the liquid and vapor phases.

4.1.2 Saponification process

Cleansers are sodium or potassium salts of long chain unsaturated fats.

At the point when triglycerides in fat/oil respond with fluid NaOH or KOH,
they are changed over into cleanser and glycerol. This is called basic
hydrolysis of esters. Since this response prompts to the arrangement of
cleanser, it is known as the Saponification procedure.
 The cleanser atom has two sections: a polar gathering (- COO-Na+) and a non-
polar gathering (R-hydrocarbon part). The polar gathering is known as the head and
the non-polar gathering is known as the tail. In this manner, the cleanser atom has a
polar head and a non-polar hydrocarbon tail. The polar head is hydrophilic in nature
(water cherishing) and the non-polar tail is hydrophobic (water repulsing) in nature.

The saponification response is exothermic in nature, since warmth is freed

amid the procedure. The cleanser shaped stays in suspension frame in the blend.
Cleanser is hastened as a strong from the suspension by adding normal salt to the
suspension. This procedure is gotten Salting out of Cleanser.
P&ID

Process Overview

By presenting fat and scathing pop arrangement in a circle shaped by

saponification reactor and reusing pump, the saponification happens in a reactor at
110° to 125°C. The reactor and the circle are warmed to likewise permit stop and
begin. Abundance saponification warmth can be expelled by circle cooling. The
saponified item is blended with spent lye which in a warmth exchanger is cooled to a
temperature of around 35°C. The cleanser leaves this phase at around 90°C and is
bolstered to the accompanying washing segment. For control of saponification manual
testing to change the alkali substance is totally satisfactory for basic reason. On the
off chance that asked for programmed control gadget of the electrolyte content by
means of pH-estimation in the cleanser release pipe of the saponification circle with
programmed metering gadget of lye are accessible.

The detachment of cleanser and glycerol by counter current fluid/fluid

extraction with saline solution happens in the washing stage. The washed cleanser is
released at the highest point of the extraction section and nourished into the fitting
stage. The glycerol spent lye is released from the base of the section in the spent lye
 consistent level bolstering vessel. A dosing pump component reuses a part of the
spent lye into the saponification arrange. By flood the over the top spent lye is
isolated and bolstered to the accompanying spent lye dissipation plant by a
dissemination pump. By including a little amount of acidic pop the curd cleanser is
fitted. This expansion is finished by a different metering pump in the metering tank
and happens specifically after the washed cleanser leaves the extractor. On the off
chance that asked for likewise an extra static or element blender can be utilized for
better homogenization. The cleanser being fitted with a little amount of cleanser and
leaving the extractor is encouraged to an isolating rotator. Here the two stages
flawless cleanser and spent lye is totally isolated from each other and is independently
released from the rotator. The spent lye is bolstered to the metering tank together with
the spent lye originating from the extractor. The slick cleanser achieves the capacity
tank and in the accompanying drying plant can be dried to the asked for drying
degree.

4.2 Economic feasibility

4.2.1 Prices of raw material for the two process

4.2.1.1 Palm Oil price

Malaysia produces about a third of all palm oil in the world. The palm
oil is produced in peninsular Malaysia as well as Borneo. Total palm oil production
in the country is around 20 million tons per year. Around 15% of the palm oil is
consumed directly in the country. Because Malaysia is so dependent on exports,
palm oil prices in Malaysia are very much driven by international supply and
demand. The price for palm oil in Malaysia is increasing by years for example the
latest price in 2016 is RM 2844.79 per metric tonne compared to ten years ago in
1996 the price is RM 1171.62 per metric tonne.
 Figure

Figure

4.2.1.2 Methanol

Since methanol is going to needed excess in the process, so a large scale of

methanol must be prepared. The price of the methanol as stated by the
Petronas methanol SDN BHD, it is RM 497.32 per metric tonne.

4.2.1.3 Sodium hydroxide (NaOH)

Sodium hydroxide is needed as the catalyst in saponification process which

caused about RM 1531.92. It is widely produce in china.

4.2.1.4 Phosphoric acid

 On the other hand, phosphoric acid is needed for acidulation process which
neutralise the alkaline medium that will cause about RM 3892.05
4.2.1.5 Zinc oxide

Zinc oxide used as the catalyst in saponification process of soap. The two
figures below shows the data of zin oxide from China.

Figure

Figure Data from China of zinc oxide

4.2.3 Economic survey

 The material used in the making of soap are oil and fats, whether animal fats
or vegetable oil, lye and catalyst. For starting, as we want to obtain oil and fats as the
basic material used, mostly the crude palm oil will be chosen as the source of fatty
acid for the soap making industry because in Malaysia there are abundance of palm
oil plantation and the company that works to produce the crude palm oil are also
many such as Sime Plantations Sdn. Bhd., United Plantation Berhad, Tradewinds (M)
Berhad, PPB Oil Palms Berhad, Kuala Lumpur Kepong Berhad (KLK), Kulim (M)
Berhad, IOI Oleochemical Industrial Berhad (largest fatty acid producer in Asia) and
many more. As stated in the www.indexmundi.com that in September 2016 that the
price of crude palm oil is RM2,844.79 per metric tonne which is 6.33% higher than in
August 2016 which is RM2675.40 and is predicted to increase more since July 2016
which is the lowest price within the last six months. It is stated in Figure 1 and Figure
2. The price has been converted to Malaysian Ringgit. The price is for palm oil with
4-5% free fatty acids.

Figure 1
 Figure 2

Palm oil is known to have about five common fatty acids which is palmitic 43
– 45%, Oleic 38-40%, Linoleic 9-11%, Stearic 4-5% and Myristic 1% which
contributes the soap hardness, stable lather, conditioning, silky feel and quicker trace.
Soap that is made up from palm oil cleans well and is also mild. However, we may try
to use the tallow from the cattle as our raw material. Based on a company from
Copenhagen, Denmark that produce it (Figure 3), they are selling tallow at a price of
300 USD per tonne which is around RM1276.59 per tonne. The product that they are
selling have a moisture content of 0.50%, total fatty acids of 90%, free fatty acids of
4%, impurities of 0.15% and iodine value of 57. But tallow from the animals that are
grain-fed and grass-fed has a big difference in their fatty acid composition.

The largest differences between the two samples were the total concentrations of
polyunsaturated fatty acids (PUFA), and the balance between the omega-3 and
omega-6 forms of these fatty acids. Grass-fed tallow had 45% less total PUFA, 66%
less omega-6 linoleic acid, and 4 times more omega-3 alpha-linolenic acid. The ratio
of omega-6 to omega-3 fatty acids was over sixteen for the grain-fed tallow but only
1.4 for the grass-fed tallow. Whatever the ratios, beef tallow is not a rich source of
polyunsaturated fatty acids, with only 3.45% in grain-fed and 1.9% of the total in
grass-fed.
 Figure 3

4.3 Other consideration

4.3.1 Energy utilization

In order to analyze the energy utilization, it must involve several calculation or

research to determine it. For this design plant, the suggestion in order to maximize the
biodiesel and glycerol production, the retrofits of distillation column was added in the
plant process flow diagram. Hence there are two case for the design of plant which are
base case and retrofitted designs of Column Grand Composite Curve (CGCC) as
identify by (Nguyen T.N, 2012). The net enthalpies for the actual and ideal operations
 at each stage are displays by the CGCC. This also recorded the minimum heating and
cooling considerations in the temperature range separation. (Nguyen T.N, 2012) also
claimed that to achieve an ideal process occur within the CGCC is the gap between
actual and the ideal must be small. By suitable retrofits, the energy losses (E x loss )
indicate ineffective use of available energy can be reduced. The causes by
irreversibility it will produce rate of entropy production in a column is directly
proportional to the rate of energy loss. The energy requirement for separation has to
increase as more thermodynamic imperfections and waste heat which due to the
energy loss has increases. Therefore, operation with less waste heat is desirable were
formed due to less energy losses generated.

Table ? comparison of operating conditions and configurations of design 1 and 2 for

distillation column.
Conditions & Design 1 Design 2
Configurations (Base Case) (Retrofitted)
No. Of Stages 4 4
Feed Stages 2 2
Feed Temperature, °C 60.40 60.37
Reflux Ratio 2 1
Condenser Duty, kW 6143.57 4135.89
Condenser 53.67 49.98
Temperature, °C
Distillation Rate, 36.97 37.09
kmol/hr
Reboiler Temperature, 297.91 297.70
°C

Table ? showed that the total energy loss or turn back reduction of total
energy loss within the retrofits design are lower compared to base cases. Condenser or
side reboiler is not affordable due to small number of stages. Besides, the design of
plant need to counter the electrical and water consumed within the plant itself. It is
mostly important for the plant to be a energy self-sufficient.

4.3.2 Process technology

In this production, it involves two process which are transesterification and

refining of the crude glycerol that has been produced as the by-product. For the
transesterification process, biodiesel is produced by the reaction with different
triglycerides. When the triglycerides are stimulated by sodium hydroxide as the
catalyst, which induce the reaction with alcohol, which in this case is the methanol or
ethanol to produce four products from the reactor before going through other process;
biodiesel, methyl ester or ethyl ester and glycerol. Biodi esel is produced using
transesterification within three reactions which di and mono-glycerides are formed as
the intermediaries. The reaction of triglycerides in fatty acid methyl esters (FAME) is
a catalysed and balanced reaction in which one mole of triglycerides reacts with three
moles of methanol. Excess of alcohol which is methanol or ethanol is needed in the
reaction medium to force the reaction and obtain a high yield.

Most industrial processes in biodiesel production use 6:1 M ratio of alcohol to

oil, with an excess of 100% of, for example methanol, in order to complete the
reaction entirely. The majority of the excess of methanol ends up in the glycerol layer
after the reaction. The majority that we are talking here is as high as 80% but the
methanol can be recovered to be used again. The most common catalysts that are
discovered for the transesterification reaction are alkaline bases. We can also use
acidic catalyst such as hydrochloric acid and sulphuric acid but commercially, all the
biodiesel production factory use sodium hydroxide or sodium methoxide.

Still we will choose sodium hydroxide to be use as it is easily obtain compared

to other catalyst and the reaction proceed faster compared using acid catalyst. Sodium
is recovered after the reaction as sodium glycerate, sodium methylate and sodium
soaps in the glycerol phase. The salts must be neutralized by using hydrochloric acid
or phosphoric acid. In this case, glycerol is obtained as an aqueous solution containing
sodium chlorate. Final purity of the glycerol is around 80 – 95%. Because sodium
hydroxide is used as the catalyst, they are generally collateral reactions forming
sodium soap. We can still purify the glycerol by using refining process which will
produce about 94% glycerol.

In transesterification, since an excess of methanol is added, two phases are

formed; one rich in methanol and one rich in biodiesel. Glycerine is distributed
between the two phases, though it is more prevalent in the methanol phase. That is the
reason why methanol is more likely to be used compared to ethanol because the
separating phase is much easier compared to ethanol due to the short polar chain.
However, recently, ethanol has become more common because it is less aggressive
compared to methanol and it is renewable. Some solid metal catalyst act as the
catalyst such as tin, zinc and magnesium. They are used as metal soap or metallic
glycolates. In this continuous process, the transesterification reaction uses a
completely heterogeneous catalyst made up of a mixture of zinc and aluminium oxide
which develops the reaction without losing the catalyst. The reaction is carried out at
a lower temperature and pressure with a homogenous catalysis, as well as excess
methanol. The excess is then removed by vaporization and recycled for the process.

Chemical conversion is reached with two successive stages of reaction and

glycerol separation in place of the balanced reaction. The catalysis section included
two fixed bed reactors fed with vegetable oil and methanol in the given proportions.
The excess of methanol is removed after each reaction by partial evaporation. Next,
the esters and glycerol are separated in a decanter. Glycerol outlets are united and
residual methanol is removed by evaporation. In order to obtain biodiesel in the
specifications desired, the last traces of methanol and glycerol have to be removed.
The methyl ester purification section of the outlet from a decanter 2 consists of a final
vaporization of methanol in a vacuum followed by final purification in an absorber to
remove soluble glycerol.

Average composition of crude glycerol generally oscillates between 40% and

70% glycerine, 10% water (in the range of 8 – 50 %), 4% salt (from 0% to 10%), less
than 0.5% methanol and approximately 0.5% free fatty acids. Crude glycerol is then
treated and refined by filtration, chemical additives and fractional distillation in
vacuum to produce various types of glycerine. It can also be refined by a method
using lower-energy intensive filtration by a series of ion exchanges in resin.

As the crude glycerol received is solid at room temperature, around 200 g of

the crude glycerol was melted at 55O℃ in a 500 ml beaker placed on a magnetic hot
plate. The molten crude glycerol under gentle stirring was acidified with different
acids (sulfuric acid, hydrochloric acid, and phosphoric acid, respectively) to a desired
pH level and was kept for a sufficiently long time to allow the formation of three
separate layers. The top layer is fatty acid phase, the middle one is glycerol rich phase
and the bottom one is inorganic slat phase. The bottom phase was separated by simple
decantation. The fatty acid-rich top phase was separated from the glycerol-rich phase
by using a separator funnel. The extracted glycerol was neutralized using 12 M
potassium hydroxide solution followed by evaporation of water at 1100℃ for 2 h and
filtration to remove the precipitated salt. The obtained glycerol was further purified by
solvent extraction process using methanol as solvent to promote the precipitation of
dissolved salts. The precipitated salts were separated by filtration and passed through
a column of activated charcoal to de-colour and remove odour and some metal ions.
 FINISHED
BIODIESEL DRYER
METHANOL

METHANOL
VEGETABLE OIL REACTOR SEPERATOR
REMOVER

NEUTRALISATION &
CATALYST (NAOH) WASHING

50% GLYCEROL

ACID WASH WATER

ACIDULATION & ACID
SEPARATION
FREE FATTY ACID WATER

METHANOL/WATER
METHANOL RETRIFICATION
CRUDE GLYCEROL 85%
REMOVER METHANOL
RECOVERY

ACIDS
WATER
HCl
ACIDULATION
H2SO4 SEPERATOR FATTY ACIDS &
METHANOL
H3PO4 INORGANIC SLATS

CRUDE GLYCEROL 95%

FILTERATION &
NEUTRALISATION EXTRACTION DECOLOURISATION
ALKALI & DEODOURISED

CRUDE GLYCEROL
99.7%
4.3.3 Safety consideration

Safety at the workplaces either while handling the hazardous chemical or

operating the equipment or machine are mostly important. As the transesterification
process by base-catalyst, it is most important to take note on something matters that
have possibility to be a hazard while the process was running. For example, there
must have standard operating procedure (SOP) in handling hazardous chemical such
phosphoric acid and methanol. The plant must be implement based on the most
suitable safety considerations correspond to the environmental condition. The design
of the plant should be provided an acceptable hazard risk to the employees and
employers. Besides the designer should know the situation or condition of the society
at surrounding. Health is the priority in our life, hence the safety of the surrounding
and awareness about this priority considerations. Every system involves in the plant
need to operate in a great manner. The manager should structure the rule or procedure
of working ethics for their workers. In addition, the plant must be conveyed with the
environmental protection requirement and any possible future restrictions.

Coconut oil on the other hand, obtained from the dried fruit of the coconut
palm tree, the fruit are dried under the sun or by burning the husks. The oil is pressed
out of the dried fruit. Based on the world oil price today, compared to all the oil that
have been said, the coconut oil is found to be the most expensive one which is
RM6355.89 per metric tonne.

As for the lye to be used, if we choose sodium hydroxide the price will be
about RM1531.91 per metric tonne and have to be import from China. China found to
be one of the largest sodium hydroxide in southeast Asia as well as potassium
hydroxide which will cause about RM3829.77 per metric tonne. There are some
factories that produce sodium hydroxide and potassium hydroxide as well but they
sell in a very low quantity that only available for school laboratory purpose. Zinc
oxide that will be used for catalyst is priced at RM9418.02 based on the price in
September 2016 at www.indexmundi.com but as for catalyst, we don’t need that
much for only catalyst purpose.
 Although making soap may seem very simple and non-dangerous
reaction, but it is not what it seems like because when you are dealing with chemical,
you must beware. There are some precaution measures that must be follow to ensure
your safety. When you are starting to conduct the saponification reaction you should
do some checklist of your safety gear for yourself totally. Firstly, if you have a long
hair, it should be tied to your back and away from your face to ensure your sight is not
blocked and your hair won’t get involved in the reaction. Safety googles should be
worn at all times to prevent your catches anything that can cause irritation. Long
sleeves shirt should be worn or it is more encouraged to wear a laboratory jacket with
long sleeves and do not fold your sleeves. Rubber gloves as well as facial mask
should be worn, strictly when you are mixing the water and lye. Apron should be
worn for extra safety. Secondly, for your environment of making the process you are
advised to cover your work area with a protective layer to avoid direct corrosion and
prepare a spray bottle filled with vinegar.

Lye is the most dangerous aspect in the soap making as it is sodium

hydroxide, for bar soaps, or potassium hydroxide for liquid soaps. Both of the
material are known to be corrosive. As we take sodium hydroxide as our lye, make
sure that all the safety measures have been done because to make aqueous sodium
hydroxide you need to mix the distilled water with the glacial sodium hydroxide.
There is one tip that has been used by many laboratory technicians and chemists, mix
your distilled water with solid distilled water (ice cubes). This is because when
mixing those solutions exothermal reaction will occur as heat is given off thus,
increase the temperature. It appears that it is very hot when we are using room
temperature distilled water. And it is the best if you don’t pour directly the lye into the
water but slowly add it by using pipette or burette. Adding too much lye into water
because it can cause volcano effect and the mixture is very corrosive. After finished
mixing, you will notice that white layer will float on top of the lye solution which is
actually impurities. It must be sieved out before pouring into the soaping oils. Lye can
also give off fumes that are extremely hazardous which cause irritation to your throat
and lungs if inhaled as well as your skin.

While mixing your lye solution, any portion spills or splashes on your skin,
start flushing your skin with cold water immediately for 15 minutes. Remove the
clothing that may have the lye solution on it. Spray your skin with vinegar to help
neutralize any lye solution that is left on your skin. After that, seek medical help.
While wait it to cool down the lye solution, make sure that it is not put at a place that
is sensitive to heat since the temperature can be up to 200℃. Keep eye on the lye
solution for several reasons such as impurities from outside might slip in, referencing
the degrees over time and to avoid crystallization of lye at the bottom of the solution.
While washing the equipment, use hot soapy water since the lye solution used is still
caustic even when mixed with oil.

Lye solution that are left must be disposed properly and shouldn’t be drained
into the sink as this will pollute the environment but make it a ‘false batter’. Mix the
solution with the vegetable oil and stir it using the spatula until it hardened you may
dispose it in the chemical wastage container. Do not dispose while it is still in liquid
form as it can break the wastage container. Last but not least, check the soap for its
pH value. Usually the soap must be between 8.5 to 10.5 pH value to be used for bath.
But there are also certain soap industry that make their soap and obtain a pH value of
5.5 to 7.
4.4 Justification of selection
Table ? Comparison Between Base-Catalyst Transesterification Vs Saponification

FACTOR BASE-CATALYST SAPONIFICATION

TRANSESTERIFICATION
Rate of reaction faster Slightly slow
Operational Temperature (50-70)°C Temperature(70-80)°C
condition Pressure 1 atm Pressure 1 atm
Raw material Palm oil, methanol, phosphoric acid, Vegetable oil, lye and
sodium hydroxide. catalyst (NaOH)
Product purity 99.36% purity of glycerol 94% purity of glycerol
Type of reactor Continuous stirred tank reactor Batch reactor
(CSTR)
Process technology Retrofits of distillation column Batch reactor
Energy utilization minimum medium
Economic aspect economically Slightly expensive

Safety level high medium

Production cost minimum medium

From table ? above, the most reliable type of reaction to apply is base-catalyst
transesterification which is in homogenous solution. The rate of reaction take place in the
system are fast. The optimum conditions are slightly lower compared to saponification. Even
the temperature is lower which it will be manipulated the rate of reaction, but the time taken
for saponification process are much slow compared to base-catalyst transesterification
process. In the addition the transesterification reaction are able to produce a high conversion
of desired product. Transesterification have an advanced technology that has retrofits
distillation column which can minimize the energy loss. Besides, in terms of economic
aspect, transesterification has use a low value of production cost and economically. Lastly,
the safety level of the transesterification’s plant design was in a good level since they are
practices a good environment of working.

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