Chapter # 1: 1.1) What Is Biodiesel?

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Chapter # 1
INTRODUCTION
1.1) What is Biodiesel?
Petro-diesel is the alkyl esters, a fraction of crude oil extracted from the earth crust. Biodiesel is
same as the petro diesel named after its origin i-e biomass defined as a fuel which is composed of
alkyl esters of long chains fatty acids also known as fatty acids alkyl esters (FAAE) include
mostly fatty acids methyl esters (FAME) derived from renewable vegetable oil, municipal waste,
animal fat or micro-algae.
Biodiesel is defined by ASTM International as a fuel composed of mono-alkyl esters of long-
chain fatty derived from renewable vegetable oils or animal fats meeting the requirements of
ASTM D6751. Vegetable oils and animal fats are principally composed of tri-acyl-glycerol
(TAG) consisting of long chain fatty acids chemically bound to a glycerol (1, 2, 3- propanetriol)
backbone. The chemical process by which biodiesel is prepared is known as the trans-
esterification reaction, which involves a TAG reaction with a short-chain monohydric
alcohol normally in the presence of a catalyst at elevated temperature to form fatty acid
alkyl esters (FAAE and glycerol). The conversion of TAG to biodiesel is a stepwise process
whereby the alcohol initially reacts with TAG as the alk-oxide anion to produce FAAE and
diacylglycerols (DAG, reaction [1], Fig. 1), which react further with alcohol (alk-oxide) to
liberate another molecule of FAAE and generate monoacylglyerols (MAG, reaction). Lastly,
MAG undergo alcoholysis to yield glycerol and FAAE (reaction, Fig. 1), with the combined
FAAE collectively known as biodiesel. Three moles of biodiesel and one mole of glycerol are
produced for every mole of TAG that undergoes complete conversion. The trans-esterification
reaction is reversible, although the reverse reaction (production of MAG from FAAE and
glycerol, for instance) is negligible largely because glycerol is not miscible with FAAE,
especially fatty acid methyl esters (FAME) when using methanol as the alcohol component.
The reaction system is biphasic at the beginning and the end of biodiesel production, as
methanol and vegetable oil and glycerol and FAME are not miscible. Methanol is most
commonly used in the commercial production of biodiesel, since it is generally less expensive
than other alcohols, but ethanol prevails in regions such as Brazil where it is less expensive than
methanol. Other alcohols aside from methanol and ethanol are also of interest for
biodiesel production because FAAE produced from higher alcohols may have different fuel
properties in comparison to methyl or ethyl esters.
A more detailed discussion of the influence of ester head group on the fuel properties of
biodiesel will be presented in a subsequent section of this report. Biodiesel are produced by the
esterification/trans esterification of lipid feedstock of various sources such as vegetable oil,
animal fat or municipal sewage sludge in the presence of acid, base, enzyme or any other solid
catalyst. Inexpensive homogenous base catalysts such as (sodium, potassium hydroxide or
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methoxide) or acid catalysts such as sulphuric acid are typically used in the commercial
preparation of biodiesel from refined or treated oils. The classic alcoholics conditions include a
TAG reaction with an excess of six molar equivalents of methanol (with respect to TAG) and 0.5
weight percent (wt.%) alkali or acid catalyst (with respect to TAG) at 50°C to 60°C for 1 h to
produce fatty acid methyl esters (FAME, biodiesel) and glycerol. The chemical composition
of biodiesel is dependent upon the feedstock from which it is produced. The fatty ester
composition of biodiesel is identical to that of the parent oil or fat from which it was produced.
A recent report (International Grains Council) indicated that rapeseed oil was the predominant
feedstock for worldwide biodiesel production in last 5 years (48%, 4.6 million metric tons,
MMT). The remaining oils included soybean (22%, 2.1 MMT) and palm (11%, 1.0 MMT),
with the rest (19%, 1.8 MMT) distributed among other unspecified vegetable oils and
animal fats. Not surprisingly, vegetable oil production and biodiesel feedstock usage are
intimately related. Feed stocks for biodiesel production vary with location according to climate
and availability. Generally, the most abundant commodity oils or fats in a particular region are
the most common feed stocks. Thus, rapeseed and sunflower oils are principally used in Europe
for biodiesel production, palm oil predominates in tropical countries, and soybean oil and animal
fats are most common in the USA. However, even combining these feed stocks do not suffice to
fully replace the volume of conventional petroleum diesel fuel (petro-diesel). Therefore,
exploration of additional feed stocks for biodiesel production has been continuously gaining
significance.
So in the troubleshooting of these issues a new source of lipid feedstock is introduced knows as
micro-algae.
1.2) Raw Material (Micro-Algae):

“A simple, non-flowering, and typically aquatic plant of a large assemblage that includes the
seaweeds and many single-celled forms. Algae contain chlorophyll but lack true stems, roots,
leaves, and vascular tissue”.
When most people think of "algae", they visualize the mat-forming growth seen on ponds, lakes,
and lagoons. This is actually mat-type cyanobacteria and is considered very unhealthy for any
waterway. Microalgae, however, are microscopic algae, typically found in freshwater and
marine systems. They are unicellular species which exist individually. Unlike higher plants,
microalgae do not have roots, stems and leaves. Microalgae, capable of performing
photosynthesis, are important for life on earth. They produce approximately half of the
atmospheric oxygen and simultaneously use the greenhouse gas, carbon dioxide (CO 2), to grow
photo-autotrophic ally. These microalgae are considered healthy for any natural waterway.
Algae are the fastest-growing plants in the world. Industrial reactors for algal culture are open
ponds, photo bioreactors and closed systems. Algae are very important as a biomass source.
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Algae will someday be competitive as a source for biofuel. Different species of algae may be
better suited for different types of fuel. Algae can be grown almost anywhere, even on sewage or
salt water and does not require fertile land or food crops, and processing requires less energy
than the algae provides. Algae can be a replacement for oil based fuels, one that is more effective
and has no disadvantages. Algae are among the fastest-growing plants in the world, and about
50% of their weight is oil. This lipid oil can be used to make biodiesel for cars, trucks, and
airplanes. Microalgae have much faster growth-rates than terrestrial crops. the per unit area yield
of oil from algae is estimated to be from 20,000 to 80,000 l per acre, per year; this is 7–31 times
greater than the next best crop, palm oil. The lipid and fatty acid contents of microalgae vary in
accordance with culture conditions. Most current research on oil extraction is focused on
microalgae to produce biodiesel from algal oil. Algal-oil processes into biodiesel as easily as oil
derived from land-based crops. [43], [44]
Table 1.1 (Oil Contents of some Micro-algae)

General Process Description:
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Fig 1.1 (General Process Description of Biodiesel)
1.3) Biodiesel Properties:

The properties of biodiesel can be grouped by multiple criteria. The most important are
those that influence the processes taking place in the engine (ignition qualities, ease of starting,
formation and burning of the fuel-air mixture, exhaust gas formation and quality and the
heating value, etc.), cold weather properties (cloud point, pour point and cold filter
plugging point), transport and depositing (Oxidative and hydrolytic stability, flash point,
induction period, microbial contamination, filterability limit temperature, etc.), wear of engine
parts (lubricity, cleaning effect, viscosity, compatibility with materials used to manufacture the
fuel system, etc.).
1.3.1) Chemical Composition of Biodiesel:

The elemental composition (carbon – C, hydrogen – H and oxygen – O), the C/H ratio and the
chemical formula of diesel and biodiesel produced from different feedstock’s is shown in Table
1.1. The elemental composition of biodiesel varies slightly depending on the feedstock it is
produced from. The most significant difference between biodiesel and diesel fuel composition
is their oxygen content, which is between 10 and 13%. Biodiesel is in essence free of sulfur.
Table 1.2 (Elemental composition of diesel fuel and biodiesel, % (m/m))

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Unlike fuels of petroleum origin, which are composed of hundreds of hydrocarbons (pure
substances), biodiesel is composed solely of some fatty acid ethyl and methyl esters; their
number depends on the feedstock used to manufacture biodiesel and is between 6 and 17. The
fatty acid methyl and ethyl esters in the composition of biodiesel are made up of carbon,
hydrogen and oxygen atoms that form linear chain molecules with single and double carbon-
carbon bonds. The molecules with double bonds are unsaturated. Thus, fatty acid esters take
the form Cnc:nd (lipid numbers), where nc is the number of carbon atoms in the fatty acid
and nd is the number of double bonds in the fatty acid (e.g., 18:1 indicates 18 carbon atoms
and one double bond). The highest concentrations are C18:1, C18:2, C18:3, followed by
C18:0. A significant exception is biodiesel from coconut oil, in the case of which the
highest concentration is C12:0, C14:0 and C16:0, hence this biodiesel is more volatile
than the others. The physicochemical properties of biodiesel produced from a given feedstock
are determined by the properties of the esters contained.
1.3.2) Cetane Number:

Cetane number (CN) is a dimensionless indicator that characterizes ignition quality of fuels for
compression ignition engines (CIE). Since in the CIE burning of the fuel-air mixture is initiated
by compression ignition of the fuel, the cetane number is a primary indicator of fuel quality
as it describes the ease of its self-ignition.
Theoretically, the cetane number is defined in the range of 15-100; the limits are given by the
two reference fuels used in the experimental determination of the cetane number: a linear-chain
hydrocarbon, hexadecane (C16H34, also called n-cetane), very sensitive to ignition, having a
cetane number of 100, and a strongly branched-chain hydrocarbon, 2,2,4,4,6,8,8-
heptamethylnonane (HMN, also called isocetane), having the same chemical formula C16H34,
with high resistance to ignition, having a cetane number of 15. The cetane number is the
percentage by volume of normal cetane in a mixture of normal cetane and HMN, which has the
same ignition characteristics as the test fuel. Thus the cetane number is given by the formula:
CN = n-cetane [%, v/v] + (0.15×HMN) [%, v/v].
Determination of the cetane number on the monocylinder engine specially designed for this
purpose (EN ISO 5165, ASTM D613) is an expensive and lengthy operation. A cheaper and
faster alternative is to determine the derived cetane number through ignition delay in a
constant-volume combustion chamber (ignition quality tester – IQT), a widely accepted method
described in ASTM D6890 and ASTM D7170, accepted by the biodiesel quality standard
ASTM D6751. The cetane number indicates ignition delay, i.e. the time elapsed since the
injection of fuel into the combustion chamber and self-ignition of the fuel-air mixture. Thus,
ignition time lag means a low cetane number and vice versa. The upper and lower limits of
the cetane number ensure the proper functioning of the engine. If the cetane number is too low,
starting the engine will be difficult, especially at low temperatures and the engine will function
unevenly and noisily, with cycles without combustion, it will warm more slowly, combustion
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will be incomplete and engine pollution will increase, especially hydrocarbon emissions. In
case of a fuel with a very high cetane number, ignition will be carried out before a proper
mix with air, resulting in incomplete combustion and the increase of the amount of exhaust
smoke. Also, if the cetane number is too high the fuel will ignite close to the injector causing it
to overheat, and unburned fuel particles can plug the injector nozzles. The optimal range of the
CN is between 41 and 56, but must not be higher than 65. The minimum cetane number of
biodiesel is 51in the European Union, 47 in the United States and 45 in Brazil. The minimum
CN for diesel oil is 40 in the USA (ASTM D 975) and 51 in Europe (EN 590). The cetane
numbers of the main pure methyl and ethyl esters are shown in Table 1.3.
Table 1.3 (Cetane number and heat of combustion for fatty acid esters)
1.3.3) Heat of Combustion:

The heat of combustion (heating value) at constant volume of a fuel containing only the
elements carbon, hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat liberated when a
unit quantity of the fuel is burned in oxygen in an enclosure of constant volume, the products
of combustion being gaseous carbon dioxide, nitrogen, sulfur dioxide, and water, with the
initial temperature of the fuel and the oxygen and the final temperature of the products at
25°C. The unit quantity can be mol, kilogram or normal square meter. Thus the units of
measurement of the heating value are KJ/kmol, KJ/kg. The volumetric heat of combustion, i.e.
the heat of combustion per unit volume of fuel, can be calculated by multiplying the mass heat
of combustion by the density of the fuel (mass per unit volume). The volumetric heat of
combustion, rather than the mass heat of combustion is important to volume-dosed fueling
systems, such as diesel engines.
The gross (or high, upper) heating value (Qg) is obtained when all products of the combustion
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are cooled down to the temperature before the combustion and the water vapor formed during
combustion is condensed. The net or lower heating value (Qn) is obtained by subtracting the
latent heat of vaporization of the water vapor formed by the combustion from the gross or
higher heating value. The net heat of combustion is related to the gross heat of combustion: Qn
= Qg – 0.2122.H, where H is the mass percentage of hydrogen in the fuel. As in internal
combustion engines the temperature of exhaust gases is higher than the boiling temperature of
water (water vapor is discharged), for assessing the heating value of the fuel, the lower heating
value of the biodiesel is more relevant. The heating value of fatty acid esters (Table 1.2)
increases with molecular chain length (with the number of carbon atoms, nc) and decreases
with their degree of unsaturation (the number of double bonds, nd). The mass heating value of
unsaturated esters is lower than that of saturated esters, but due to their higher density, the
volume heating value of unsaturated esters is higher than that of saturated esters. For example,
methyl stearate (nd=0) has a mass heating value of 40099 KJ/kg, and methyl oleate (nd=1) has
40092 KJ/kg. Reported to the volume unit, the heating value of methyl stearate is 34070
KJ/L, while the volume heating value of methyl oleate is 34320 KJ/L. The presence of
oxygen in the esters molecules decreases the heating value of biodiesel by 10-13% compared
to the heating value of diesel fuel. Due to the fact that fuel dispensing in CIE is volumetric, the
energy content of the injected dose will be more reduced in the case of biodiesel,
therefore, the specific fuel consumption for biodiesel will be higher. This is partially
compensated by the fact that the density of biodiesel is higher than that of diesel fuel.
1.3.4) Biodiesel Density:

Fuel density (ῥ) is the mass of unit volume, measured in a vacuum. Since density is strongly
influenced by temperature, the quality standards state the determination of density at 15 °C.
Fuel density directly affects fuel performance, as some of the engine properties, such as cetane
number, heating value and viscosity are strongly connected to density. The density of the fuel
also affects the quality of atomization and combustion. As diesel engine fuel systems (the
pump and the injectors) meter the fuel by volume, modification of the density affects the
fuel mass that reaches the combustion chamber, and thus the energy content of the fuel
dose, altering the fuel/air ratio and the engine’s power. Knowing the density is also necessary in
the manufacturing, storage, transportation and distribution process of biodiesel as it is an
important parameter to be taken into account in the design of these processes. The density
of esters depends on the molar mass, the free fatty acid content, the water content and the
temperature. Density values determined for pure esters are presented in Table 1.3. The density
of biodiesel is typically higher than that of diesel fuel and is dependent on fatty acid
composition and purity. As biodiesel is made up of a small number of methyl or ethyl esters
that have very similar densities, the density of biodiesel varies between tight limits.
Contamination of the biodiesel significantly affects its density; therefore density can also be an
indicator of contamination.
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Table 1.4 (Density and viscosity of fatty acid esters)
1.3.5) Biodiesel Viscosity:

The viscosity of liquid fuels is their property to resist the relative movement tendency of their
composing layers due to intermolecular attraction forces (viscosity is the reverse of fluidity).
Viscosity is one of the most important properties of biodiesel. Viscosity influences the ease of
starting the engine, the spray quality, the size of the particles (drops), the penetration of the
injected jet and the quality of the fuel-airmixture combustion. Fuel viscosity has both an upper
and a lower limit. The fuel with a too low viscosity provides a very fine spray, the drops having
a very low mass and speed. This leads to insufficient penetration and the formation of black
smoke specific to combustion in the absence of oxygen (near the injector). A too viscous
biodiesel leads to the formation of too big drops, which will penetrate to the wall opposite to the
injector. The cylinder surface being cold, it will interrupt the combustion reaction and blue
smoke will form (intermediate combustion product consisting of aldehydes and acids with
pungent odor). Incomplete combustion results in lower engine power. Too high viscosity leads
to the increase of combustion chamber deposits and the increase of the needed fuel
pumping energy, as well as the increased wear of the pump and the injector elements due to
higher mechanical effort. Too high viscosity also causes operational problems at low
temperatures because the viscosity increases with decreasing temperature (for temperatures at
or below -20 °C viscosity should be at or below 48 mm2/s). Viscosity also influences the
lubricity of the fuel as some elements of the fuel system can only be lubricated by the fuel
(pumps and injectors). Due to the presence of the electronegative oxygen, biodiesel is more
polar than diesel fuel; as a result, the viscosity of biodiesel is higher than that of diesel fuel.
The viscosity of pure ethyl esters are higher then, viscosity of methyl esters (Table 1.3).
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1.3.6) Cold flow properties:

Generally, all fuels for CIE may cause starting problems at low temperatures, due to worsening
of the fuel’s flow properties at those temperatures. The cause of these problems is the
formation of small crystals suspended in the liquid phase, which can clog fuel filters partially or
totally. Because of the sedimentation of these crystals on the inner walls of the fuel system’s
pipes, the flow section through the pipes is reduced, causing poor engine fueling. In extreme
situations, when low temperatures persist longer (e.g. overnight), the fuel system can be
completely blocked by the solidified fuel.
The cloud flow performances of the fuels can be characterized by the cloud point (CP), the
pour point (PP), the cold filter plugging point (CFPP) and viscosity. An alternative to CFPP is
the low-temperature flow test (LTFT). Recently, the U.S. introduced a new method for
assessing the cold flow properties ofbiodiesel, called cold soak filtration test (CSFT).
Table 1.5 (Cold flow properties of biodiesels from different feed stoks)
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1.3.6.1) Cloud point: (CP)

The cloud point (CP) is the temperature at which crystals first start to form in the fuel. The
cloud point is reached when the temperature of the biodiesel is low enough to cause wax
crystals to precipitate. Initially, cooling temperatures cause the formation of the solid wax
crystal nuclei that are submicron in scale and invisible to the human eye . Further decrease
of temperature causes these crystals to cloud point. The cloud point because the crystals
form a cloudy suspension. Below the CP these crystals might plug filters or drop to the
bottom of a storage tank. The CP is the most commonly used measure of low-temperature
operability of the fuel. The biodiesel cloud point is typically higher than the cloud point of
conventional diesel. The cloud point of biodiesel depends on the nature of the feedstock it was
obtained from and is between -5 °C (ALME) and 17 °C (TME).
1.3.6.2) Pour point: (PP)

The pour point is the temperature at which the fuel contains so many agglomerated crystals that
it is essentially a gel and will no longer flow. This occurs if the temperature of the biodiesel
drops below CP, when the microcrystals merge and form large clusters, which may disrupt
the flow of the biodiesel through the pipes of the engine’s fuel system. Similarly to the cloud
point, the pour point values also depend on the feedstock the biodiesel was produced from (see
Table 1.4). Pour point values are between -15 °C (REE and YMEE) and 16 °C (PME).
Although CP and PP are relatively easily determined, they only provide indicative values for
the minimum temperature at which the fuel can be used. While at cloud point the fuel can still
be used in acceptable conditions, at pour point this is no longer possible. In other words, cloud
point overestimates minimum operating temperature and pour point underestimates it.
1.3.6.3) Cold filter plugging point: (CFPP)
The cold filter plugging point is the lowest temperature at which 20 mL of fuel passes through a
filter within 60s by applying a vacuum of 2KPa. The CFPP test employs rapid cooling
conditions. For this reason, CFPP does not reflect the actual limit of the fuel’s operability
temperature. The test does not take into account the fuel systems specially designed to operate at
low temperatures (heavy-duty vehicles and some light-duty vehicles). Nevertheless, most
standards require the determination of this parameter and its value is regulated depending on
the climatic conditions of each region or country. The values of the CFPP of biodiesel produced
from various feed stocks are listed in Table 1.4. CME has the lowest value, while TME has the
highest. Biodiesel produced from the most common feedstock’s has inferior cold flow properties
compared to conventional diesel fuel (has a higher cloud point and pour point compared to
petroleum diesel), which can lead to operational issues in cold climates, such as filter plugging
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due to wax buildup or reduced fuel flow. Conventional diesel blends with 10 % (v/v)
biodiesels typically have significantly higher CP, PP and CFPP than petroleum diesel fuel.
1.3.6.4) Low-temperature flow test: (LTFT)
Although CFPP is accepted almost worldwide as the minimum temperature at which fuel
can be exploited, mainly because of the rapid cooling of the sample, the test does not entirely
reflect real cooling conditions of the fuel. The Low-Temperature Flow Test (LTFT) is a
similar attempt to the test determining the CFPP, the major difference being the cooling speed
of the fuel sample, which in this case is 1 °C/h, reflecting more accurately the real conditions,
when for example the fuel in the fuel system of a vehicle is cooled over a frosty night. In
determining the low temperature flow temperature the sample volume is 180 mL, the filter is
finer, and the vacuum filtration pressure is higher. Like CFPP, LTFT is defined as the lowest
temperature at which 180 mL of fuel safely passes through the filter within 60 s. Since the LTFT
is not included in biodiesel quality standards, currently there is very limited information about
its values for biodiesel (see Table 1.4).
1.3.6.5) Cold soak filtration test (CSFT)

This test is the newest requirement under ASTM D6751, added in 2008 in response to data
indicating that in blends with petroleum diesel of up to 20% some biodiesels could form
precipitates above the cloud point. Some substances that are or seem to be soluble at ambient
temperature come out of the solution if temperature decreases or biodiesel is stored at ambient
temperature for a longer period. This phenomenon was observed both in the case of pure
biodiesel and its blends with diesel fuel. Solid or semi-liquid substances can, in turn, cause
filter clogging. The CSFT allows highlighting this danger and improving biodiesel due to this
phenomenon. Cold soak consists of chilling a 300 ml sample for 16 hours at 4 °C, then
warming it up to ambient temperature (68-72 ºF, 20-22 °C) and filtering with a 0.7 micron
glass fiber filter with a stainless steel filter support. The result of this test is filtering time.
There are two time limits for filtration: in the case of net biodiesel for use throughout the year,
the filtration time is 360 seconds or less; if the seller claims the post-blended biodiesel is fit
for use in temperatures below 10 ºF (-12 °C) the filtration time is 200 seconds or less. The test
result depends mainly on the type and quality of the used feedstock, the purity of biodiesel,
the soap value, the total glycerin, etc. The higher the soap value, the higher the cold soak
filtration results. In addition it was found that total glycerin can also negatively influence the
cold soak filtration results. When the total glycerin is within the ASTM
6751standards.Because CSFT has only recently been included in biodiesel quality standards, at
present there is very little reported data on this parameter (Table 1.4).
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1.3.7) Biodiesel lubricity:

Lubricity describes the ability of the fuel to reduce the friction between surfaces that are under
load. This ability reduces the damage that can be caused by friction in fuel pumps and injectors
(Schumacher, 2005). Lubricity is an important consideration when using low and ultra-low
sulfur fuels (ULSD). The fuel lubricity can be measured with High Frequency Reciprocating Rig
(HFRR) test methods as described at ISO 12156-1. The maximum corrected wear scar diameter
(WS 1.4) for diesel fuels is 460 μm (EN 590). Reformulated diesel fuel has a lower lubricity and
requires lubricity improving additives (which must be compatible with the fuel and with any
additives already found in the fuel) to prevent excessive engine wear. The lubricity of biodiesel
is excellent. Biodiesel may be used as a lubricity improver. The lubricity of some biodiesels
and the influence of biodiesel concentration on this parameter in blends with diesel fuel are
shown in Table 1.5. The lubricity of biodiesel depends on the feedstock it is produced from.
Biodiesel from jatropha oil has the highest and biodiesel sunflower oil has the lowest lubricity.
Generally, it can be stated that 1% (v/v) biodiesel mixed with ultra-low sulfur diesel fuel
(ULSD) already provides lubricity that meets the requirements of the commercial diesel fuel’s
lubricity quality standards
Table 1.6 (The effect of the biodiesel additive in ULSD on WS1.4 (µm))
1.3.8) Flash point: (FP)

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The flash point is the minimum temperature calculated to a barometric pressure of 101.3KPa
at which the fuel will ignite (flash) on application of an ignition source under specified
conditions. It is used to classify fuels for transport, storage and distribution according to
hazard level. The flash point does not affect the combustion directly; higher values make fuels
safer with regard to storage, fuel handling and transportation. FP varies inversely with the
fuel’s volatility. For biodiesel the minimum flash point is 93°C in the United States, 100 °C
in Brazil and 120 °C in Europe. Biodiesel’s flash point decreases rapidly as the amount of
residual (un-reacted) alcohol increases (methanol’s flash point is 11–12 °C, and
ethanol’s is 13–14 °C). Thus, measuring the biodiesel flash point helps indicate the presence
of methanol or ethanol. For example, the presence of 0.5% methanol in biodiesel reduces
biodiesel flash point from170 °C to 50 °C. If flash point is used to determine the methanol
content, the ASTM standard imposes for it a minimum value of 130 °C. This limit may be
considered too severe, because at the maximum permissible concentration of methanol of
0.2% w/w biodiesel flash point drops below 130 °C. The flash point of biodiesel produced
from various feed stocks is presented in Table 1.6.
Table 1.7 (Flash point, acid value, and iodine value and oxidation stability of biodiesels from
different feedstock)
1.3.9) Acid value:

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The acid value (AV), also called neutralization number or acid number is the mass of
potassium hydroxide (KOH) in milligrams that is required to neutralize the acidic
constituents in one gram of sample. The acid value determination is used to quantify the
presence of acid moieties in a biodiesel sample. In a typical procedure, a known amount of
sample dissolved in organic solvent is titrated with a solution of potassium hydroxide with
known concentration and with phenolphthalein as a color indicator. The acidic compounds that
could possibly be found in biodiesel are:
 Residual mineral acids from the production process

 Residual free fatty acid from the hydrolysis process or the post- hydrolysis process of
the esters
 Oxidation byproducts in the form of other organic acids.
This parameter is a direct measure of the content of free fatty acids, thus the corrosiveness of
the fuel, of filter clogging and the presence of water in the biodiesel. A too high amount of
free glycerin can cause functioning problems at reduced temperatures and fuel filter clogging.
This parameter can also be used to measure the freshness of the biodiesel. Fuel that has
oxidized after long-term storage will probably have a higher acid value.
1.3.10) Iodine value:

The iodine value (IV) or iodine number was introduced in biodiesel quality standards for
evaluating their stability to oxidation. The IV is a measurement of total unsaturation of
fatty acids measured in g iodine/100 g of biodiesel sample, when formally adding iodine to
the double bonds. Biodiesel with high IV is easily oxidized in contact with air. The iodine
value highly depends on the nature and ester composition of the feed stocks used in biodiesel
production. Therefore the IV is limited in various regions of the world depending on the
specific conditions: 120 in Europe and Japan, 130 in Europe for biodiesel as heating oil, 140 in
South Africa, in Brazil it is not limited and in the U.S., Australia and India it is not included in
the quality standard (it would exclude feed stocks like sunflower and soybean oil).
Biodiesel with high IV tends to polymerize and form deposits on injector nozzles, piston rings
and piston ring grooves. The tendency of polymerization increases with the degree of
unsaturation of the fatty acids.
1.3.11) Biodiesel stability:

Biodiesel quality can be affected by oxidation during storage (in contact with air) and
hydrolytic degradation (in contact with water). The two processes can be characterized by the
oxidative stability and hydrolytic stability of the biodiesel. Biodiesel oxidation can occur during
storage while awaiting distribution or within the vehicle fuel system itself. The stability of
biodiesel can refer to two issues:
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 Long-term storage stability or aging.

 Stability at elevated temperatures or pressures as the fuel is recirculated through an
engine’s fuel system.
For biodiesel, storage stability is highly important. Storage stability refers to the ability of
the fuel to resist chemical changes during long term storage. These changes usually
consist of oxidation due to contact with oxygen from the air.
Biodiesel composition greatly affects its stability in contact with air. Unsaturated fatty acids,
especially the polyunsaturated ones (e.g. C18:2 and C18:3) have a high tendency to oxidation.
After oxidation, hydro peroxides (one hydrogen atom and 2 oxygen atoms) are attached to the
fatty acid chain. Oxidation reactions can be catalyzed by some of the materials present (the
material the reservoir is produced from) and light. After the chemical oxidation reactions
hydro-peroxides are produced that can, in turn, produce short chain fatty acids, aldehydes, and
ketones. Hydrogen per oxides can polymerize forming large molecules. Thus, oxidation
increases the viscosity of biodiesel. In addition, oxidation increases acid value, the color
changes from yellow to brown, solid deposits can form in the engine fuel system (pipes and
filters), the lubricity and heating value of the biodiesel is reduced.
When water is present, the esters can hydrolyze to long chain free fatty acids, which also cause
the acid value to increase. These acids can catalyze other degradation reactions such as reverse
trans-esterification and oxidation. The water required for hydrolysis can be present as a
contaminant. For determining the oxidation stability of biodiesel two types of tests are
currently used:
 The Rancimat test

 The oxidative stability index (OSI)
The Rancimat test method is an accelerated oxidation test in which the biodiesel to be tested is
run at elevated temperatures (110 °C) whilst exposing the sample to a stream of purified
air (10 L/hour) accelerating the oxidation process of the oil. After passing through the
biodiesel, the air is fed into a collection flask containing distilled water and a probe to
measure conductivity. As the biodiesel sample degrades, the volatile organic acids produced
are carried to the collection flask, and the conductivity of the solution is recorded by the
probe. Oxidation stability will be given by the induction period, defined as the time between
the start of the test and the sudden conductivity increase of the solution in the collection flask.
This results in auto-oxidation in a few hours, instead of months.
16
The oxidative stability index (OSI) is another measurement method of the conductivity
increase caused by the formation of secondary products in the oxidation process. The OSI is
defined as the time until the conductivity of a biodiesel sample rises most rapidly during an
accelerated oxidation test. The oxidation of biodiesel is influenced by its composition
(increases with the level of unsaturation of fatty acids in its composition), i.e. the feedstock
used to manufacture the biodiesel. For example, the content of oleic acid methyl ester in the
case of biodiesel produced from sunflower oil may vary between 48 and 74%. In addition, the
induction period of biodiesel made from rapeseed oil is 12 times greater than those obtained
from soybean oil and 25 times higher than those produced from linseed oil. The presence of
metals (the tank walls and metals contained in the biodiesel) can accelerate the oxidation
process, whereas sulfur is an antioxidant. Oxidation stability can be improved by using the
appropriate additives. Additives such as tert-butylhydroquinone (TBHQ), butylated
hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PrG) and alpha-
tocopherol (vitamin E) have been found to enhance the storage stability of biodiesel.
Biodiesels produced from some feedstocks (e.g. soybean oil) naturally contain some
antioxidants. Any fuel that will be stored for more than 6 months, whether it is diesel fuel or
biodiesel, should be treated with an antioxidant additive.
1.3.12) Water and sediments:

Water content is a purity indicator for the biodiesel. Biodiesel should be dried after water
washing to get the water specification below 500 ppm (0.050 %). Even when biodiesel is dried
properly by the producer, water can accumulate during storage and transportation.
The moisture accumulated in biodiesel leads to the increase of free fatty acid concentration,
which can corrode metal parts of the engine’s fuel system. Biodiesel is much more
hygroscopic (it attracts water) than diesel oil. The biodiesel absorbs water during storage when
the temperature is higher and the water absorbed is precipitated at lower temperatures.
Following these repeated processes, the accumulated water is deposited on the bottom of the
tank. Water in biodiesel facilitates microbial growth and the formation of sediments. To
measure the water and sediment content, a 100 mL sample of undiluted fuel
iscentrifuged at a relative centrifugal force of 800 for 10 minutes at 21 to 32°C (70 to
90°F). After centrifugation, the volume of water and sediment which has settled into the tip of
the centrifuge tube is read to the nearest 0.005 mL and reported as the volumetric percent of
water and sediment.
1.3.13) Other Properties:
Sulfated ash is a measure of ash formed from inorganic metallic compounds. After the burning
of biodiesel, in addition to CO2 and H2O a quantity of ash is formed consisting of unburned
hydrocarbons and inorganic impurities (e.g. metal impurities). Metallic ash is very abrasive and
17
may cause excessive wear of the cylinder walls and the piston ring.
Carbon residue indicates the presence of impurities and deposits in the engine combustion
chamber, and is also an indicator of the quantity of glycerides, free fatty acids, soaps and trans-
esterification reaction catalyst residues. [40], [41], [42], [46]
1.4) Biodiesel Applications:

 It provides a market for excess production of vegetable oils and animal fats. There is
increasing demand around the world for soybean meal to provide the protein for human
and animal consumption. If new markets are not found for the soybean oil, then the price
will be low and farmers will have even more difficulty producing a profit.
 It decreases the country's dependence on imported petroleum. Though the percentage
of the country's fuel supply that can be replaced with biodiesel would be small, an
additional source of fuel can have a surprising impact on fuel price stability.
 It is renewable and does not contribute to global warming due to its closed carbon cycle.
Carbon in the fuel was originally removed from the air by plants so there is no net
increase in carbon dioxide levels.
 It provides substantial reductions in carbon monoxide, unburned hydrocarbons, and
particulate emissions from diesel engines. Some emissions tests have shown slight oxide
of nitrogen (NOx) increase with biodiesel. New research on real-time vehicles has
shown a decrease in NOx emissions.
1.5) Advantages and Disadvantages of Biodiesel:
Biodiesel is a clean source of energy. It can be included in green energy as biodiesel has many
environmental, economic advantages but in return it has few of disadvantages also.
1.5.1) Advantages:
Biodiesel has attracted considerable interest as an alternative fuel or extender for petro-diesel
for combustion in compression–ignition (diesel) engines. Biodiesel is miscible with petro-diesel
in any proportion and possesses several technical advantages over ultra-low sulfur diesel fuel
(ULSD, <15 ppm S), such as inherent lubricity, low toxicity, derivation from a renewable and
domestic feedstock, superior flash point and biodegradability, negligible sulfur content, and
lower overall exhaust emissions.
1.5.2) Disadvantages:
18
Important disadvantages of biodiesel include high feedstock cost, inferior storage and oxidative
stability, lower volumetric energy content, inferior low-temperature operability versus petro
diesel, and in some cases, higher NOx exhaust emissions.
Many of these deficiencies can be mitigated through cold flow improver and antioxidant
additives, blending with petro-diesel and/or reducing storage time. Additional methods to
enhance the low- temperature performance of biodiesel include crystallization fractionation and
trans-esterification with long- or branched-chain alcohols. Strategies to improve the exhaust
emissions of biodiesel, petro-diesel, and blends of biodiesel in petro-diesel include various
engine or after-treatment technologies such as selective catalytic reduction (SCR), exhaust gas
recirculation (EGR), diesel oxidation catalysts, and NOx or particulate traps. However,
feedstock acquisition currently accounts for over 80% of biodiesel production expenses, which
is a serious threat to the economic viability of the biodiesel industry. One potential solution to
this problem is employment of alternative feed stocks of varying type, quality, and cost. These
feed stocks may include soap-stocks, acid oils, tall oils, used cooking oils, and waste restaurant
greases, various animal fats, non-food vegetable oils, and oils obtained from trees and
microorganisms such as algae. However, many of these alternative feed stocks may contain
high levels of free fatty acids (FFA), water, or insoluble matter, which affect biodiesel
production.
1.6) Monitoring the Biodiesel Quality:

Biodiesel quality can be provided efficiently if its entire manufacturing process is monitored:
from monitoring feedstock acidity, assuring complete separation of biodiesel from glycerin, to
removing the excess of alcohol and contaminants before its marketing. Quality assurance and
monitoring should include storage, testing, blending and distribution. Fuel quality monitoring
is conducted by independent laboratories that can accredit manufacturers, distributors and
quality analysis laboratories.
1.7) Process Available and Capacity Selection:
1.7.1) Process Available:
The common process in all available processes is the trans-esterification of lipid feedstock
obtained from vegetable oil, animal fat or municipal sewage sludge. Trans-esterification may be
occur using three types of catalyst, which are:
1. Enzyme-catalyzed trans-esterification
2. Base-catalyzed trans-esterification
3. Acid-catalyzed trans-esterification
19
The overall process of trans-esterification by using different catalysts (enzymes base or an acid)
is same but the factors which may vary by using different types of catalysts includes:
 Mechanism of trans-esterification reaction

 Product quality
 Cost
 Side product generation such as soap in alkali catalyzed trans-esterification
1.7.1.1) Enzyme-catalyzed trans-esterification:
Enzyme-catalyzed trans-esterification for the production of Biodiesel is not preferable as

compare to acid- catalyzed because of the following reasons:
 Low reaction rate.

 Enzyme cost for industrial scale use in comparison to alkali catalyst and acid catalyst.
 Low enzyme stability in the presence of excess methanol.
 Enzyme catalyzed trans-esterification is not well organized and the R & D work being done
on it.
1.7.1.2) Base-catalyzed trans-esterification:

Base-catalyzed trans-esterification for the production of Biodiesel is also not preferable now a
day as compare to acid-catalyzed because of the following reasons:
 Soap formation due to the presence of FFA in large quantity

 Decreased efficiency of catalyst
 Corrosion of the reactor and pipelines by dissolved acid/base species, which inevitably
raises the material cost for process construction.
 Impossibility of catalyst recovery from the reactant-product mixture. Catalyst separation
can only be achieved by neutralizing the remaining catalysts and disposing of them at the
end of `the reaction, which raises problems with environmental pollution.
 Limitation
 In establishing a continuous process. For these reasons, the heterogeneously catalyzed
process, especially using solid base catalysts, has been studied continuously for the last
decade.
1.7.1.3) Acid-catalyzed trans-esterification:

Acid-catalyzed trans-esterification for the production of Biodiesel is preferable now a days as
compare to other catalyzed trans-esterification (enzyme & base) because of the following
reasons:
20
 Directly produce biodiesel from low-cost lipid feedstock, generally associated with high
FFA Concentrations.
 No soap formation.
 Low Cost.
 Catalyst recovery is possible in an easy manner.
 High reaction rate
 High catalyst efficiency
1.7.2) Process Selection:

So, the preferred process among the above discussed processes is continuous acid-catalyzed
trans- esterification so the high quality, low cost without any side product (undesirable) may
achieved. Also, as our raw material is micro-algae which contain high proportion of TAG’s, so
we strongly recommend the acid catalyzed trans-esterification so as to avoid the soap formation.
In the lipid feed stock obtained from the micro-algae after processing from the Expeller
and Solvent Extractor contains 20% FFA’s and 80% of TAG’s (Triacylglycerol) and in the
esterification process 20% of FFA and 80% of TAG converted into Biodiesel to gives the
desired product with the efficiency of 99% of esterification process. The products obtained are
Mono alkyl esters (Biodiesel), H2O and Glycerol. The Glycerol is the by product and has an
economical value so glycerol is also a value added product of this esterification process.
Two main sections are in process selection:
 Process Description
 Process Flow Diagram
1.7.2.1) Process Description:

1. Algae Transportation
2. Expulsion of Algal Oil
3. Lipid Extraction (Leaching)
4. Solvent Recovery
5. Trans-esterification
6. Separation of Methanol (Distillation)
7. Neutralization and Separation
8. Washing of Biodiesel
9. Glycerol & Biodiesel Phase Separation
10. Separation of Biodiesel from H2O via Evaporation (Final product)
11. Separation of Glycerol from H2O via Evaporation (Value-added product)
21
1.7.2.1.1) Algae Transportation:

The first step in the Biodiesel production is the transportation of raw material (dried micro-
algae) in the Expulsion unit. Generally, micro-algal ponds are built in sea-sides due to the
concern of large water requirements while biodiesel production sites are in the city. Therefore,
prior to using the micro-algae to produce biodiesel, the dewatered (dried) micro-algae from the
dryers has to be transported to the biodiesel production site.
1.7.2.1.2) Expulsion:
The dewatered micro-algae (55% solids content and 45% Lipid content) transported from
algal cultivation plant will be passed through expeller in which 75% of the lipid contents in the
micro-algae are extracted. [26], [3]
1.7.2.1.3) Lipid Extraction (Leaching):
The solid biomass is powdered with mixing machine. A solvent hexane, exhibited a good
performance of oil extraction from sludge. Therefore, the powdered dried sludge was mixed
(150 rpm) with the solvent mixture of hexane for 1h at 50°C in a lipid extractor unit. The
solvent used is must be the 3 times of the remaining lipid content in solid biomass and the
extraction efficiency is 99.5% in the lipid extracted. After extraction, the solid biomass are
separated out from the bottom of the extractor while the mixed stream of solvent and lipids are
send to the distillation column for the solvent recovery. [3], [26], [25]
1.7.2.1.4) Solvent Recovery (Distillation):

The mixed solution of lipids and hexane from extraction will be sent to distillation column for
solvent recovery. The distillation column is operated at 80°C temperature to completely
separate the solvent (hexane) as the boiling point of hexane is 68.73°C. 100% solvent is
recovered in this process and which is again re-used for the further extraction of lipids from
solid biomass.
1.7.2.1.5) Trans-esterification:
Trans-esterification is the key step of biodiesel production. In micro-algal biodiesel production,
acid catalyst is used because of the fact that oil contains a large portion of free fatty acids
which would lead to soap formation if base is used as a catalyst. In trans-esterification reactor,
the oil obtained from the extraction step is mixed with methanol and sulfuric acid (3%
sulfuric acid) in methanol to lipid molar ratio of 6:1. The excess addition of methanol in the
process is to enhance the conversion. The reaction will proceed at 80°C under mixing and the
trans- esterification efficiency is 99%. [30], [31], [5], [48]
22
1.7.2.1.6) Separation of Methanol (Distillation):

After the reaction, the mixture will go to distillation for methanol recovery (99.2% recovery
efficiency) and the recovered methanol will be then mixed with fresh methanol and injected
back to the reactor.
1.7.2.1.7) Neutralization and Separation:

In order to neutralizer the action of sulphuric acid, we added some quantity of base CaO in a
reactor. The amount of added base is depend upon the amount of catalyst used in the reactor.
Solid particles of CaSO4 are formed in neutralizer which is further separated by action of gravity
from the product stream. [47], [48], [49]
1.7.2.1.8) Biodiesel Purification/Washing:

To separate biodiesel from glycerol, hot water is added in the product stream, the temperature in
the washer will be at 55°C for better separation of biodiesel from glycerol. The residue (mixture
of biodiesel, glycerol, and unreacted lipids) of the distillation (methanol recovery) will be sent to
washing tank in which hot water (55°C) (obtained from flue gas cooling in microalgae
cultivation system) is present. [35], [27]
1.7.2.1.9) Biodiesel and Glycerol Phase Separation:
The phase separation on Biodiesel and glycerol occur due to density difference which is:
Biodiesel density = 883.4 Kg/m3
Water density = 1000 Kg/m3
Glycerol density = 1261 Kg/m3
Due to high density of glycerol, it remains at the bottom of the tank. Top product is the
Biodiesel and intermediate is the water. So, by decantation process glycerol can be separate
from Biodiesel.
In the last two steps two evaporators:
One for the separation of Biodiesel from water and second for the separation of remaining
glycerol from biodiesel are used for the further purification of Biodiesel and after that the Final
Product of the desired quality (99.5%) and composition i-e Biodiesel is obtained. [35], [27]
23
24
25
1.7.4) Capacity Selection:

1.7.4.1) Capacity:-
Capacity means that how much quantity of desired product should be produce in a specific
period of time so as to easily design and operate the plant efficiently.
1.7.4.2) Capacity Selection Criteria:-
Its major dependency is on following two factors:
1. Need as per National/International or Regional level
2. Raw Material availability
1.7.4.2.1) National/Region wise need:
Biodiesel is used as a fuel with blending of it to natural diesel/furnace oil up to a certain level.
There are different standards of biodiesel which are used according to the requirement. [36]
1. B5 (5% biodiesel, 95% petroleum-diesel)
4. B100 (100% biodiesel)
Pure biodiesel (B100) can be used in vehicles which are particularly designed for biodiesel. B20
can be used in petroleum-diesel operating vehicles with a little modification in the engine.
According to the report of the Oil Companies Advisory Committee (OCAC) 2008, Pakistan
consumes around 8 million tons of diesel and 7.2 million tons of furnace oil per year. [37] It
means Pakistan consumes 15.2 million tons of furnace and diesel oil per year. So, 3.04 million
tons of biodiesel per year would be required for B20 fuel mixture.
8+7.2 MT 20 3.04 MT
× =
year 100 year
3.04 MT 1 year 106 Tons 1000 Kg 8.328767 ×106 Kg 8328.767 T

× × × = =
year 365 days 1 MT Ton day day
So, Pakistan’s biodiesel consumption is 8328.76 tons per day. If we produce 10,000 liter of
biodiesel per day (LPD) then,
Density of Biodiesel is 883.4 Kg/m3. [36]
10000 Liters 883.4 Kg 1 m3 8834 Kg 8.834 T

× 3
× = =
Day m 1000 Liters day day
8834 Kg day 368.08 Kg
¿ × =
day 24 h h
We have to produce 8.310 tons of Bio-diesel per day.
26
8.834 T / day
× 100=0.11 %
8328.767 T /day
So, by producing 10,000 LPD Biodiesel, we can contribute 0.11% of total demand of biodiesel
for B20 fuel of Pakistan.
Likewise, for University of Gujrat, we can also calculate the demand of biodiesel for running its
transport on B20 fuel. According to the Transport Office, University of Gujrat, 2400 liters of
diesel is required to run its 80 buses daily.
The density of petroleum diesel is 834 Kg/m3. [36]
2400 Liters 834 Kg m3 20 400.32 Kg

× 3
× × =
day m 1000 liters 100 day
400.32 Kg/day
×100=4.53 %
8834 Kg/day
So, UOG requires 400.32 Kg of biodiesel per day which is the 4.53% of our total production.
1.7.4.2.2) Raw Material Availability:
To produce 10,000 LPD biodiesel, we have to calculate that how much micro-algae would be
required and form where it would come. There are many species of micro-algae but we select
Bacillariophyta, as it contains about 20-50% lipid contents and in good growing conditions it
usually gives 40-50% lipid contents. We are taking avg. 45% of lipid content in this specie of
micro-algae. [37] The other major necessities for growing micro-algae are given below: [38]
According to trans-esterification reaction in reactor (R-1), 365.26 Kg/h of lipids is required.
For this amount of lipids, 812.70 Kg/h of Algae is required. [38]
Basis for calculation of amount of micro-algae to produce required biodiesel: [38]
Kg Kg
ρalgae =0.25 3
; Lipid Content =45 % ; Lipids Density=920 3 ;
m m
Pond Depth=0.5 m; Harvesting Rate=25 %
365.26 Kg m3 0.3970 m 3
Lipids Required= × =
h 920 Kg h
0.3970 m3 100 g biomass 920 Kg Kg

Algae Required= × × 3
=812.70
h 45 g lipids m h
To harvest 25% Biomass of micro-algae every day, we must maintain 3250.8 Kg/h biomass
(micro-algae) in the system.
27
812.70 Kg/h Kg
Biomass∈the System= =3250.8
0.25 h
3250.8 Kg m3 24 h 312089.88m 3 ML
Water Required= × × = =312.08
h 0.25 Kg day day day
312089.88 m 3 of Water 2
Pond Length= =624179.77 m =62.41 hectares
0.5 m depth of pond
3250.8 Kg 1000 1.302 Kg/h
Biomass productivity= × =
h 624179.77 m2
m2
Summarize Data: [38]
Sr. No. Components Quantity
1 Biodiesel Production 368.08 Kg/h
2 Required micro-algae 812.70 Kg/h
3 Micro-algae required in the system 3250.8 Kg/h
4 Water required for Micro-algae 312.08 ML/day
5 Land for required Micro-algae production 62.41 ha
6 Biomass Productivity 1.302 Kg/h.m2
Table 1.8 (Specification Sheet of Capacity Selection)
We can install somewhere near the coastal area of Pakistan because the easily available saline
water from sea. Land for foot ponds is also readily available. Other nutrient and condition of
sunlight is also observed before selecting the site for algae cultivation.
28
Chapter # 2
MATERIAL BALANCE
In chemical industries, the material balance is the key to find out the product quantity as well as
quality. It ensures a process is going well or not.
The material balance is the fundamental tool of chemical engineering. It is the basis for the
analysis and design of chemical processes. So it goes without saying that chemical engineers
must thoroughly master its use in the formulation and solution of chemical processing
problems.
In chemical processing we deal with the transformation of raw materials of lower value into
products of higher value and, in many, cases unwanted byproducts that must be disposed of.
In addition many of these chemical compounds may be hazardous. The material balance is the
chemical engineer's tool for keeping track of what is entering and leaving the process as well as
what goes on internally. Without accurate material balances, it is impossible to design or
operate a chemical plant safely and economically.
The General mass transfer equation is,

¿
So in order to precede this project, material balance on the following equipment is to be carried
out:
1. Expeller (C-1)
2. Extractor (E-1)
3. Distillation Column (D-1)
4. Reactor (R-1)
6. Neutralizer (N-1)
7. Separator (S-1)
8. Pre-Heater (H-1)
9. Water Washing (W-1)
10. Phase Separator (S-2)
11. Evaporator (V-1)
12. Evaporator (V-2)
29
2.1) Expeller Balance: (C-1)
As in general mass balance equation (2.1),

Accumulation = 0
This is a non-reactive system so,
Rate of mass∈¿ Rate of mass out

Product Stream C-1= 538.42 Kg/h
75% Extraction Remaining lipids= 91.42 Kg/h

Total Biomass= 812.70 Kg/h
of Lipid Solids= 446.98 Kg/h
Lipid content= 365.72 Kg/h (45%)
Contents by
Solid content= 446.98 Kg/h (55%)
Expeller (C-1)
Extracted Lipids= 274.28 Kg/h
Overall Balance:
812.70 Kg 538.42 Kg 274.28 Kg
= +
h h h
Lipid Balance:
365.72 Kg 91.42 Kg 274.28 Kg
= +
h h h
Solid Balance:
446.98 Kg 446.98 Kg
=
h h
2.2) Extractor Balance: (E-1)

Accumulation = 0

30
Total Biomass Out= 447.45 Kg/h

Remaining Biomass= 538.42 Kg/h
Lipid content= 91.43 Kg/h (45%) Lipids= 0.46 Kg/h
99.5% Extraction
Solid content= 446.98 Kg/h (55%) Solids= 446.98 Kg/h
of remaining
Lipid Contents
by Extractor (E-
Hexane (Solvent) = 403.83 Kg/h 1) Product from E-1 = 494.79 Kg/h
Lipids= 90.97 Kg/h

Hexane= 403.83 Kg/h
Overall Balance:
538.42 Kg 403.83 Kg 447.45 Kg 494.80 Kg 942.25 Kg
+ = + =
h h h h h
Lipid Balance:
91.43 Kg 90.97 Kg 0.46 Kg
= +
h h h
Solid Balance:
446.98 Kg 446.98 Kg
=
h h
Hexane Balance:
403.83 Kg 403.83 Kg
=
h h
2.3) Distillation Column: (D-1)
The Boiling point based separation of Hexane from lipids is done via Distillation as there is big
boiling point difference between these two. 100% hexane is recovered through this process.
B.P of Hexane = 68˚C

B.P of Lipids = 295˚C

Accumulation = 0
31
Hexane = 403.83 Kg/h
100% Solvent
Recovery is done
by Distillation
Product from E-1 = 494.79 Kg/h
Column (D-1)
Lipids= 90.97 Kg/h
Hexane= 403.83 Kg/h
Temp. = 70˚C
Lipids = 90.97 Kg/h
It is recommended to use distillation column for 100% recovery of hexane form lipids.
Overall Balance:
494.79 Kg 403.83 Kg 90.97 Kg
= +
h h h
2.4) Reactor: (R-1)

Reaction conversion efficiency in trans-esterification reactor is 99%. It means 1% lipids which
are entered in the reactor remains unreacted.
365.26 Kg 3.65 Kg
Unreacted Lipid Contents= × 0.01=
h h
361.60 Kg
Total Lipids=365.36 – 3.65= will react ∈thereactor .
h
Composition of lipid stock is, [13]
 80% Triglycerides (TAG’s)

 20% Free Fatty Acids (FFA’s)
The lipid content extracted form Bacillariophyta (Micro-algae) is mainly consist of these carbon
chains. [13]
32
 C14 (Myristic Acid) : 32%

 C16 (Palmitic Acid) : 42%
 C20 (Arachidic Acid) : 26%
Biodiesel=Fatty Acids of Methyl Esters( FAME)
3.4.1) 80% of TAG’s:
1 mole + 3 mole → 3 mole + 1 mole

This is the general trans-esterification reaction for TAG’s.
Formulas:
% of TAG
Mass Flow rate of a TAG Component=Total Lipids ×
100
Mass Flow rate
No .of Moles=
Molecular Mass
Mass Flow rate=No . of moles × Molecular Mass
Table 2.1
TAG % of Molecular Mass No. of moles Methanol FAME Glycerol

Component TAG Mass Flow rate Kmol/h Required produced Produced
Comp. Kg/Kmol Kg/h Kg/h Kg/h Kg/h
C14 32 779.29 92.57 0.119 11.40 86.24 10.93
C16 42 807.32 121.50 0.150 14.44 122.13 13.85
C20 26 863.32 75.21 0.087 8.36 25.205 8.02
Total 100 - 289.28 0.356 34.215 293.577 32.79
33
Molecular Masses:
Components Molecular Mass (Kg/Kmol)

C15 (FAME) 242
C16 (FAME) 270.5
C21 (FAME) 236
Methanol 32
Glycerol 92
Table 2.2
3.4.2) 20% of FFA’s:
1 mole + 1 mole → 1 mole + 1 mole

This is the general trans-esterification reaction for FFA’s.
Formulas:
% of FFA
Mass Flow rate of a FFA Component=Total Lipids ×
100
Mass Flow rate
No .of Moles=
Molecular Mass
Mass Flow rate=No . of moles × Molecular Mass
Table 2.3
FFA % of Molecular Mass No. of moles Methanol FAME Water

Component FFA Mass Flow rate Kmol/h Required produced Produced
Comp. Kg/Kmol Kg/h Kg/h Kg/h Kg/h
C14 32 228.37 23.143 0.101 3.243 24.52 1.824
C16 42 256.41 30.375 0.118 3.79 32.04 2.132
C20 26 318.49 18.80 0.059 1.89 19.24 1.062
Total 100 - 72.321 0.279 8.93 75.815 5.02
34
For the better conversion of lipids into biodiesel, Methanol is used in 6:1 to the lipids. Total
Kmol of Lipids required for 99% conversion of chemical reaction:
0.356 Kmol 0.279 Kmol 0.635 Kmol
Total Lipids= + =
h h h
For 6 Methanol to 1 Lipid ratio,
0.635 Kmol 3.812 Kmol
Total Methanol Rreqired= ×6=
h h
3.812 Kmol 32 Kg 121.97 Kg
TMR= × =
h Kmol h
121.97 Kg 43.14 Kg 78.83 Kg
Remaining Methanol= − =
h h h
Total Products out from the Reactor:
Components Mass Flow rate (Kg/h)

FAME’s 369.39
Glycerol 32.79
Water 5.02
Unreacted lipids 3.65
Catalyst 14.62
Excess Methanol 78.83
Total 504.30
Table 2.4
Methanol = 121.97 Kg/h 35
jvi
99% conversion of
lipids into FAME’s
Lipids = 365.26 Kg/h in Reactor (R-1)
Temp. = 80˚C
Product from R-1 = 504.30 Kg/h
Pressure = 400KPa
FAME = 369.39 Kg/h
Reaction time = 4h
Glycerol = 32.79 Kg/h
Catalyst (H2SO4) = 14.62 Kg/h Methanol to Lipid Methanol = 78.83 Kg/h
Ratio is 6:1 Unreacted Lipids = 3.65 Kg/h
Water = 5.019 Kg/h
Catalyst = 14.62 Kg/h
Overall Balance:
121.97 Kg 365.26 Kg 14.62 Kg 504.30 Kg
+ + =
h h h h
The recovery of methanol from product stream is done via Distillation as there is considerable
boiling point difference between methanol and other components of product. 99.2% excess
methanol is recovered through this process and which is reprocess to the reactor with blending
of some fresh amount of methanol in order to maintain the balance.
B.P of Methanol = 68˚C

B.P of unreacted Lipids = 295˚C
B.P of FAME = 304˚C
B.P of Glycerol = 290˚C
B.P of water = 100˚C

Accumulation = 0
36
Top Product D-2 = 78.24 Kg/h
Methanol = 78.20 Kg/h

Water = 0.04 Kg/h
99.2% Methanol
Recovery is done
by Distillation
Product from R-1 = 504.30 Kg/h
Column (D-2)
FAME = 369.39 Kg/h Bottom Product D-2 = 426.06 Kg/h
Temp. = 80˚C
Methanol = 78.83 Kg/h FAME = 369.39 Kg/h
Unreacted Lipids = 3.65 Kg/h Glycerol = 32.79 Kg/h
Water = 5.019 Kg/h Methanol = 0.63 Kg/h
Catalyst = 14.61 Kg/h Unreacted Lipids = 3.65 Kg/h
Water = 5.019 Kg/h
Catalyst = 14.61 Kg/h
Overall Balance:
504.30 Kg 78.24 Kg 426.06 Kg
= +
h h h
Methanol Balance:
78.83 Kg 78.20 Kg 0.63 Kg
= +
h h h
Water Balance:
5.02 Kg 0.04 Kg 4.98 Kg
= +
h h h
Other components which are FAME, Glycerol, Unreacted lipids and Catalyst were remain in the
bottom stream in exactly same fractions.
2.6) Neutralizer: (N-1)

Acid base reaction is done in a neutralizer reactor in order to nullify the effect of acid by adding
a strong base. Reaction conversion efficiency of the reactor is 100% means all acid and added
base will convert into salts and water.
37
Chemical Reactions in the Neutralizer:
H 2 O+CaO →Ca ( OH )2 ∆ H=−62 KJ /mol
H 2 S O 4 + Ca(OH )2 → CaS O 4 +2 H 2 O ∆ H=−13 KJ /mo
Overall reaction:
H 2 S O 4 + CaO →CaS O 4 + H 2 O ∆ H=−75 KJ /mol
1 mole+1 mole → 1mole +1 mole
According to reaction, when 1 mole of sulfuric acid is react with 1 mole of calcium hydroxide
then 1 mole of calcium sulfate and 1 mole of water produced.
14.62 Kg of H 2 S O 4 Kmol
No .of moles= × =3.579 Kmol
h 98 Kg
Now,
H 2 S O4 + CaO →CaS O4 + H 2 O
0.145 Kmol+0.145 Kmol→ 0.145 Kmol+0.145 Kmol
0.145 Kmol 56 Kg 8.35 Kg

CaO required ∈reaction= × =
h Kmol h
0.145 Kmol 136.1 Kg 20.30 Kg
CaS O 4 produced= × =
h h h
0.145 Kmol 18 Kg 2.684 Kg
Water Produced= × =
h Kmol h
Bottom Product D-2 = 426.06 Kg/h
FAME = 369.39 Kg/h Neutralizer (N-1)

Glycerol = 32.79 Kg/h Product from N-1 = 434.43 Kg/h
Methanol = 0.63 Kg/h 100% Conversion of
Unreacted Lipids = 3.65 Kg/h acid FAME = 369.39 Kg/h
Water = 5.019 Kg/h Glycerol = 32.79 Kg/h
Temp. 80˚C
Catalyst = 14.61 Kg/h Methanol = 0.63 Kg/h
Unreacted Lipids = 3.65 Kg/h
Water = 7.663 Kg/h
CaSO4 = 20.30 Kg/h
Base (CaO) = 8.35 Kg/h
38
Overall Balance:
426.06 Kg 8.35 Kg 434.43 Kg
+ =
h h h
2.7) Separator: (S-1)

Separator is a device which is use to separate two or more components of a material. The
separator is primarily worked on the principal of sedimentation. Solid particles of CaSO4 are
separated in this equipment from liquid.
Product from N-1 = 414.13 Kg/h
100% Separation FAME = 369.39 Kg/h

of CaSO4 Glycerol = 32.79 Kg/h
Product from N-1 = 434.43 Kg/h Methanol = 0.63 Kg/h
Separator (S-1)
FAME = 369.39 Kg/h Water = 7.663 Kg/h
Water = 7.663 Kg/h CaSO4 = 20.30 Kg/h
CaSO4 = 20.30 Kg/h
Overall Balance:
434.43 Kg 414.13 Kg 20.30 Kg
= +
h h h
2.8) Water Washer: (W-1)

Water is added in to the Separated product to further separate the biodiesel form glycerol. Water
makes two difference phases and then we separate them using density difference phenomena.
39
Water is preheated to 38.5˚C before adding to the product so that the Temp of mixed stream
reached at 55˚C which is the favorable condition for separation. Water to FAME ratio is 1:2 in
the unit. [35]
369.39 Kg 1 184.70 Kg
Water ¿ be added= × =
h 2 h
Product from S-1 = 414.13 Kg/h
FAME = 369.39 Kg/h Water Washer

Glycerol = 32.79 Kg/h Product from W-1 = 598.82 Kg/h
W-1
Unreacted Lipids = 3.65 Kg/h FAME = 369.39 Kg/h
Temp. = 55˚C
Water = 192.36 Kg/h
Added Water = 184.70 Kg/h
Overall Balance:
414.13 Kg 184.70 Kg 598.82 Kg
+ =
h h h
Water Balance:
7.663 Kg 184.70 Kg 192.36 Kg
+ =
h h h
2.9) Phase Separator: (S-2)

Two phase are being formed in the previous unit, Biodiesel-water phase and Glycerol-water
phase. The two phases are separated easily due to the difference in the density of these two
phases.
Biodiesel Density = 884.3 Kg/m3
Water Density = 1000 Kg/m3
Glycerol Density = 1261 Kg/m3
40
FAME Water phase = 468.63 Kg/h

99.65% of
Biodiesel is FAME = 368.1 Kg/h
Product from W-1 = 598.82 Kg/h Glycerol = 0.066 Kg/h
Separator in
FAME = 369.39 Kg/h Unreacted Lipids = 3.65 Kg/h
Glycerol = 32.79 Kg/h Water = 96.18 Kg/h
Phase Separator
(S-2)
Water = 192.36 Kg/h
Glycerol Water Phase = 130.20 Kg/h

Water = 96.18 Kg/h
FAME = 1.292 Kg/h
Overall Balance:
598.82 Kg 468.63 Kg 130.20 Kg
= +
h h h
FAME Balance:
369.39 Kg 368.1 Kg 1.292 Kg
= +
h h h
Glycerol Balance:
32.79 Kg 0.066 Kg 32.73
= +
h h h
Water Balance:
192.36 Kg 96.18 Kg 96.18 Kg
= +
h h h
2.10) Evaporator: (V-1)

41
Evaporated (V-1) is used to remove additional water and methanol by providing heat. Water is
continuously evaporated at 110˚C so that 99.5% pure biodiesel is extracted as a final product
from this unit.
Top product V-1 = 96.81 Kg/h
99.5% pure
Biodiesel is Methanol = 0.63 Kg/h
obtained Water = 96.18 Kg/h
FAME Water phase = 468.63 Kg/h
Temp. = 110˚C
FAME = 368.1 Kg/h
Glycerol = 0.066 Kg/h Evaporation Unit
Methanol = 0.63 Kg/h (V-1) Bottom product V-1 = 371.81 Kg/h
Water = 96.18 Kg/h FAME = 368.1 Kg/h
Overall balance:
468.63 Kg 96.81 Kg 371.81 Kg
= +
h h h

Evaporated (V-2) is used to remove additional water from Glycerol (By Product) by providing
heat. Water is continuously evaporated at 110˚C.
Water = 96.81 Kg/h

100% Removal
of Water
Glycerol Water Phase = 130.20 Kg/h Temp. = 110˚C

Evaporation Unit
Glycerol = 32.73 Kg/h (V-2)
Water = 96.18 Kg/h
FAME = 1.292 Kg/h Bottom product V-2 = 371.81 Kg/h

FAME = 1.292 Kg/h
Overall balance:
42
130.20 Kg 96.81 Kg 371.81 Kg

= +
h h h
2.12) Overall Energy Balance:
Overall Mass
Total Input = 1064.1 Kg/h Balance Total Output = 1064.1 Kg/h
Micro-algae = 812.70 Kg/h FAME = 369.39 Kg/h

Methanol = 43.72 Kg/h Methanol = 0.63 Kg/h
Catalyst = 14.61 Kg/h Unreacted Lipids = 3.65 Kg/h
CaO = 8.35 Kg/h Water = 192.36 Kg/h
CaSO4 = 20.30 Kg/h
Solid Biomass = 447.44 Kg/h
Overall balance:
Total Input=Total Output
1064.1 Kg 1064.1 Kg
=
h h
43
Chapter # 3
ENERGY BALANCE
According to law of conservation of energy:
[Rate of Accumulation of Energy within system =Rate of Energy entering the system – Rate of
Energy leaving the system + Rate of Energy generation] … (4.1)
For steady state system no accumulation of mass or energy within system, so by
modifying Above equation, and applying across equipment’s, the energy balance of equipment is
as under. The datum temperature is taken as 25ᵒC.
The equipment’s on which energy balance is applied are:
1. Extractor (E-1)
3. Reactor (R-1)
5. Neutralizer ( N-1)
6. Pre-Heater ( H-1)
7. Evaporator (V-1)
8. Evaporator ( V-2)
3.1) Extractor: (E-1)
Hexane (Q1) = 187699.5 KJ/h Biomass Out (Q3) = 24150.94 KJ/h

Extractor
E-1
Temp. = 50ᵒC
Remaining Lipids (Q2) = 0 KJ/h Heaxne + Oil (Q4) = 28437.88 KJ/h
Energy Input:
As, Datum Temperature = 25ᵒC
Lipids & Hexane Enter at Datum Temperature and atmospheric pressure.
44
Mass Specific Heat Capacity (Using Hysis):

Cp of Hexane = 2.246 KJ/KgᵒC
Cp of Lipids = 2.011 KJ/KgᵒC
Energy input with Hexane (Recycled stream from D-1):
Q2=m*Cpl*(Tb.p-Tdet.) + m* λ + m*Cpg*(T-Tb.p)
= 403.81*[2.47*(68.73-25) + 335.5 + 1.908*(80-68.73)] = 187699.5 KJ/h
Energy input with lipids:
Q2 = m*Cp*ΔT = 538.41*2.011*(25-25) = 0
Total Energy input = 0
Energy output:
Mass Specific Heat Capacity (Using Hysis):
Cp of Hexane + Oil = 2.299 KJ/KgᵒC
Cp of Biomass = 2.159 KJ/KgᵒC
Hexane + oil and Biomass leaves at 50ᵒC
Energy output with biomass:
Q3 = m*Cp*ΔT = 447.44*2.15*(50-25) = 24150.92 KJ/h
Energy output with (Hexane + oil):
Q4 = m*Cp*ΔT = 494.78*2.29*(50-25) = 28437.88 KJ/h
Total Energy output = 24150.92 + 28437.88 = 52588.82 KJ/h
Required Energy = Energy Output – Energy Input = 52588.82 – 187699.5 = -135111 KJ/h
(Negative Sign Shows the cooling process is required in the system)
45
Top Product D-1 (Q2) = 187699.5 KJ/h
Hexane + Oil (Q1) = 28499.73 KJ/h

Distillation Column
D-1
80ᵒC
Bottom Product D-1 (Q3) = 10872.8 KJ/h
Energy Input:
Mass flow rate of oil = Hexane = 494.78 Kg/h
Cp of mixture = 2.304 KJ/KgᵒC
Temperature of mixture = 50ᵒC
Temperature Difference = ∆T = (50-25) = 25ᵒC
Q1 = m*Cp*∆T = 494.78*2.304*25 = 28499.73 KJ/h
Energy Output:
For Hexane,
Mass flow rate of Hexane = 403.81Kg/h.
Cp of liquefied Hexane = 2.47 KJ/KgᵒC
Cp of gaseous phase Hexane = 1.908 KJ/KgᵒC
Latent Heat = λ = 335.3 KJ/Kg
Distillation column temperature = T = 80ᵒC
Hexane boiling point = Tb.p = 68.73ᵒC
Q2=m*Cpl*(Tb.p-Tdet.) + m* λ + m*Cpg*(T-Tb.p)
46
= 403.81*[2.47*(68.73-25) + 335.5 + 1.908*(80-68.73)] = 187699.5 KJ/h

For Lipids:
Mass flow rate of lipids = 90.97 Kg/h
Cp of lipids = 2.1 KJ/KgᵒC
T = 80ᵒC
∆T = T-Tdet = 80-25 = 55ᵒC
Q3 = m*Cp*∆T = 90.97*2.1*55 = 10872.58 KJ/h
Total Heat out = 187699.5 + 10872.58 = 198572.08 KJ/h

Required Energy = Energy Output – Energy Input = 198572.58 – 28437.88 = 170072.4 KJ/h
3.3) Reactor: (R-1)
Total Lipids (Q1) = 10458.93 KJ/h
Reactor
Methanol (Q2) = 11364.17 KJ/h R-1 Product R-1 (Q4) = 70090.37 KJ/h
Temp. = 80ᵒC
Pressure
400KPa
Catalyst (Q3) = 0 KJ/h
Energy Input:
For Lipid’s:
47
Mass flow rate of lipids = 365.26Kg/h

Cp of lipids = 2.008 KJ/Kg ᵒC
T = 39.69ᵒ C
∆T = 55-39.69 = 14.27ᵒC
Q1 = m*Cp*∆T = 365.26*2008*14.27 = 10458.93 KJ/h
For Sulphuric acid:
Mass flow rate of Sulphuric acid = 14.61 Kg/h
Cp = 1.34 KJ/KgᵒC
T = 25ᵒC
∆T = 25-25 = 0
Q2 = m*Cp*∆T = 14.61*1.34*0 = 0
For Methanol (Recycled stream from (D-2) + Fresh Methanol:

Mass flow rate of Methanol = 121.96 Kg/h
Cp = 3.60 KJ/KgᵒC
T = 64.48ᵒC
∆T = 64.48-25 = 39.48 ᵒC
Q3 = m*Cp*∆T = 121.96*3.60*39.48 ᵒC = 11364.17 KJ/h
Total heat in = 10458.93 KJ/h
Energy Output:
Mass flow rate of output product = 504.30 Kg/h
Cp = 2.52 KJ/KgᵒC
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q4 = m*Cp*∆T = 504.30*2.52*55 = 70090.37 KJ/h
48
Top Product D-2 (Q) = 92457.99 KJ/h
Methanol Q2 = 92448.73 KJ/h

Distillation
Water Q3 = 9.259 KJ/h
Product from R-1 (Q1) = 60715.4 KJ/h Column
D-2
Temp. = 80ᵒC
Bottom Product D-2 (Q4) = 49866.27 KJ/h
Energy Input:
Mass flow rate of Total Product R-1= 504.30 Kg/h
Cp = 2.189 KJ/KgᵒC
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q1= m*Cp*∆T = 504.30*2.189*55 = 60715.4 KJ/h
Energy Output:
For Methanol;
Mass flow rate of Methanol = 78.199 Kg/h
Cpliquid = 1.466 KJ/KgᵒC
Cpgas = 1.50KJ/KgᵒC
Tb.p = 64.65ᵒC
T = 80ᵒC
λ = 1101 KJ/Kg
49
Q2 = m*Cp*∆T = m [Cpliquid (Tb.p-Tdet) + λ + Cpgas (T- Tb.p)]
= 78.199*[1.466*(64.65-25) + 1101 + 1.50*(80-64.65)] = 92448.73 KJ/h
For Water:
Mass flow rate of water = 0.04015 Kg/h
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q3 = m*Cp*∆T = 0.04015*4.193*55 = 9.25 KJ/h
Total Energy output for Top Product= Q2+ Q3= 92448.73 + 9.25 = 92457.99 KJ/h
For Bottom product:

Mass flow rate = 426.06 Kg/h
Cp = 2.12 KJ/KgᵒC
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q4 = m*Cp*∆T = 426.06*2.12*55 = 49866.27 KJ/h
Total Energy output (Top + Bottom) = 92457.99 + 49866.27= 1142324.26 KJ/h

3.5) Neutralizer: (N-1)
Bottom from D-2 (Q1) = 49866.27 KJ/h Product from N-1 (Q) = 51317.7 KJ/h
Neutralizer Unreacted Product (Q3) = 49866.27 KJ/h

CaSO4 (Q4)= 1451.422 KJ/h
N-1
Temp. = 80ᵒC
50
CaO (Q2) = 0 KJ/h
Heat of Reaction (Qr) = 35.74 KJ/h

Energy Input:
For Bottom Product:
Cp = 2.12 KJ/KgᵒC
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q1 = m*Cp*∆T = 426.06*2.12*55 = 49866.27 KJ/h
For CaO Input:

Cp = 0.75 KJ/KgᵒC
T = 25ᵒC
∆T = 25-25 = 0
Q2 = m*Cp*∆T = 8.35*0.75*0 = 0
Energy Output:
Product from N-1:
Mass flow rate for unreacted Product = 426.06 Kg/h
Cp = 2.12 KJ/KgᵒC
T = 80ᵒC
∆T = 80-25 = 55ᵒC
Q3 = m*Cp*∆T = 426.06*2.12*55 = 49866.27 KJ/h
Mass flow rate for CaSO4 = 20.3 Kg/h
Cp = 1.3 KJ/KgᵒC
T = 80ᵒC
51
∆T = 80-25 = 55ᵒC
Q4 = m*Cp*∆T = 20.3*1.3*55 = 1451.45 KJ/h
Q= Q3 + Q4 = 49866.27 + 1451.45 = 51317.72 KJ/h
For heat of reaction:

Mass flow rate of CaSO4 = 20.3 Kg/h
∆HCaO = 1.33 KJ/Kg
∆HCaSO4 = 0.421 KJ/Kg
∆HTotal = ∆HCaO + ∆HCaSO4 = 1.33 + 0.421 = 1.76 KJ/Kg
Qr = m*∆HTotal = 20.3*1.76 = 35.74 KJ/h
Total Heat Out = Q + Qr = 513117.72 KJ/h + 32.74 KJ/h = 51353.44 KJ/h
3.6) Pre-Heater: (H-1)
Pre-Heater
Added Water (Q1) = 0 KJ/h Hot Water (Q2) = 10542.1 KJ/h
H-1
Temp. = 38.5ᵒC
Energy Balance around Pre-Heater:

Mass flow rate of water added = 184.69 Kg/h
Cp = 4.18 KJ/KgᵒC
52
T = 25ᵒC
∆T = 25-25 = 0
Q1 = m*Cp*∆T = 184.69*4.18*0 = 0
Energy Output:
Mass flow rate of heated water = 184.69 Kg/h
Cp = 4.22 KJ/KgᵒC
T = 38.5ᵒC
∆T = 38.5-25 = 13.5ᵒC
Q2 = m*Cp*∆T = 184.69*4.22*13.5 = 10542.1 KJ/h
Required Energy = Energy Output – Energy Input = 10542.1 – 0 = 10542.1 KJ/h
Top Product V-1 (Q) = 250078 KJ/h
Evaporator Methanol (Q2) = 797.5 KJ/h

FAME water phase (Q1) = 34430.16 KJ/h Water (Q3) = 249280.5 KJ/h
V-1
Temp. = 110ᵒC Bottom Product (Q4) = 69751.22 KJ/h
Energy Input:
Mass flow rate of FAME water phase = 468.62 Kg/h
Cp = 2.44 KJ/KgᵒC
T = 55ᵒC
∆T = 55-25 = 30ᵒC
Q1 = m*Cp*∆T = 468.62*2.44*30 = 34430.16 KJ/h
53
Energy Output:
For Methanol;
Mass flow rate of methanol = 0.603 Kg/h
Cpgas = 1.57 KJ/KgᵒC
Tb.p = 64.65ᵒC
T = 110ᵒC
λ = 1101 KJ/Kg
= 0.603*[3.75*(64.65 – 25) + 1101 + 1.57*(110 – 64.65)] = 797.5 KJ/h
For Water:
Mass flow rate of water = 96.13 Kg/h
Cpgas = 2.081 KJ/KgᵒC
Tb.p = 100ᵒC
T = 110ᵒC
λ = 2256 KJ/Kg
= 96.13*[4.2*(100-25) + 2256 + 2.081*(110-100)] = 249280.5 KJ/h
Total Top Product Energy output:
Q = Q2 + Q3 = 797.5 + 249280.5 = 250078 KJ/h
Energy output for Bottom Product:

54
T = 110ᵒC
∆T = 110-25 = 85ᵒC
Q4 = m*Cp*∆T = 371.81*2.207*85 = 69751.22 KJ/h
Total Energy output = 250078 + 69751.22 = 319829.22 KJ/h
Water (Q2) = 249280.5 KJ/h
Evaporator
Glycerol water phase (Q1) = 14807.33 KJ/h
V-2
Bottom Product V-2 (Q3) = 7899.46 KJ/h

Temp. = 110ᵒC
Energy Input:
Mass flow rate of Glycerol Water phase = 130.19 Kg/h
T = 55ᵒC
∆T = 55-25 = 30ᵒC
Q1 = m*Cp*∆T = 130.19*3.79*30 = 14807.33 KJ/h
Energy Output:
For Top Product;
Mass flow rate of top product = 96.18 Kg/h
Cp liquid = 4.2 KJ/KgᵒC
Cp gas = 2.081 KJ/KgᵒC
55
Tb.p = 100ᵒC
T = 110ᵒC
λ = 2256 KJ/Kg
= 96.18*[4.2*(100-25) + 2256 + 2.081*(110-100)] = 249280.5 KJ/h
For Bottom product;

Mass flow rate of glycerol = 34.017 Kg/h
Cp = 2.73 KJ/KgᵒC
T = 110ᵒC
∆T = 110-25 = 85ᵒC
Q3 = m*Cp*∆T = 34.017*2.73*85 = 7899.46 KJ/h
Total Energy output= = 249280.5 + 7899.46= 257179.96 KJ/h

56
Chapter # 4
EQUIPMENT DESIGN
Equipment designing is a key part of a chemical engineering project. We select four different
equipment for designing, which are as follow;
1. Reactor (R-1)
3. Heat Exchanger (H-1)
4. Evaporator (E-1)
4.1 Reactor Design: (R-1)
Continuous type reactor is to be selected as to compensate the requirement of Biodiesel
demand. There is algal lipid feedstock so, for the proper mixing of lipid feedstock and
methanol a mixer is lowered as a CSTR (Continuous Stirred Tank Reactor). Because,
 Conversion efficiency for Algal lipid feed is 99%.

 Continuous to meet the today’s demand.
 For handling large amounts of lipid feed.
 Proper mixing so as to have a higher forward rate reaction.
Conversion (XA) = 99% and Reaction time (t) = 4 hours [31]
4.1.1) Calculation of Basic Design Parameters:

Mass Flow Rate
Molar Flow Rate=
Molecular Weight
Mass Flow Rate
Volumetric Flow Rate=
Density
Table (4.1)
Component Mass Flow Molecular Molar Flow Density Volumetric
Rate (Kg/h) Weight Rate (Kg/m3) Flow Rate
(Kg/Kgmol) (Kmol/h) (m3/h)
TAG’s 289.287 816.64 0.3542 935 0.3092
FFA’s 72.321 267.75 0.2701 843.2 0.0857
Methanol 121.79 32 3.8059 793 0.1535
57
4.1.2) Reaction Kinetics: (Rate Constant and Rate of Reaction)

As the trans-esterification reaction is step wise reaction, it completes in three steps, first one
mole of triglycerides react with one mole of methanol to form one mole of di-glycerides and one
mole of FAME and hence reaction continues till the end as follows;
Triglycerides+ Methanol → Methayl Ester ( FAME )+ Diglycerides….. (A)
Diglycerides+ Methanol → Methayl Ester ( FAME ) + Monoglycerides….. (B)
Monoglycerides+ Methanol → Methayl Ester ( FAME ) +Glycerol….. (C)
Overall reaction is as follows;

Triglycerides+ 3 Methanol → 3 Methayl Ester ( FAME ) +Glycerol…… (O)
As rate of overall reaction is determined by the rate of slowest reaction, hence conversion of TG
to DG is the slowest reaction. [50] These reactions are 2nd order reactions.
Rate Constant and Rate of reaction can be calculated by following formulas of 2nd order kinetics.
For 2nd Order Reaction [51], [52]
A+ B → Products
C Bo
−r A =k C A C B=k C 2Ao (1−X A )( M −X A ) …. (4.1) Where , M =
C Ao
Molar Flow Rate
Concentration C Ao=
Volumetric Flow Rate
C A=C Ao ×(1−X A )
For Reaction A;
Methanol required for this reaction is,
Total Methanol−Reacting Methanol 121.79−87.57 Kg
Methanol Req .= = =11.40
3 3 h
Table (4.2)
Component Molar Flow Volumetric Initial Conc. Final C Bo
Rate Flow Rate (CAo , CBo) Concentration M=
C Ao
(Kmol/h) (m3/h) (Kmol/m3) (CA , CB)
(Kmol/m3)
TAG’s 0.3542 0.3093 1.1449 0.011449 21.6443
Methanol 0.3563 0.0143 24.7812 - -
58
Rate Constant: (k)

Graph between ln(CB/CA) on y-axis and tim (t) on x-axis will tell as the rate constant of the
reaction. [51], [52]
As its total 4 hour operation, at inlet and outlet conditions;
Table (4.3)
ln(CB/C
T
A)
3.07474
0
3
4.46982
4
6
Slope=k (C Bo −C Ao )
(Fig. 4.1) For Rate Constant (k)

5
4.5
f(x) = 0.35 x + 3.07
R² = 1
4
Ln(CB/CA)
3.5
2.5
2
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Time In 'h'
Fig 4.1 (Graph between ln(CB/CAo) and Time)

Slope 0.3488 Kmol
k= = =0.014757 3
(C Bo−C Ao) (24.7812−1.1449) m s
Rate of Reaction: (-rA)
From equation (4.1), we have
−r A =( 0.01475)×¿
59
Kmol
−r A =0.0039955
m3 s
4.1.3) Volume of Cylindrical Reactor: (Vc)

Reactor volume can be calculated by the multiplying reacting fluids volume and reaction time.
Where reaction time (t) is the same as the residence time (τ ). [53]
VC
τ= ….. (4.2)
vr
Total reacting volume of fluids will be (vr) = VTAG’s + VFFA’s + VMethanol + VCatalyst
m3
v r=0.3093+ 0.0857+0.1535+0.00794=0.55668
h
V c =0.55668 × 4=2.2267 m3=2226.7 L=588.24 Gallons
For Actual Reactor Volume, (12% excess volume)
V C =1.12 ×V R=1.12 ×2.2267=2.4939 m3=2493.9 L
4.1.4) Reactor Size: (L & D)

For Cylindrical Shells, the standard Length to Diameter ratio is in range 1 to 3. [53], [54]
So, we take,
L = 2.4D
We know that, cylindrical shell volume is equal to,
π π
V =π ×r 2 L= × D 2 L= × D 2 × ( 2.4 D ) =0.6 π × D 3
4 4
V 3 2.4939
D=
√
3
0.6 π √
=
1.884
=1.098 m=3.601 ft =43.21∈¿ 1098 mm
And Length is,

L=2.4 D=2.4 × 1.098=2.6352 m=8.6434 ft=103.72∈¿
4.1.5) Total Volume of Reaction: (V)
60
Total Volume of the reactor will be equal to volume of cylindrical shell and two heads (top and
bottom). We select the hemispherical heads at top and bottom of the reactor to attain maximum
possible excess volume and area for the reacting fluids and to avoid flooding. [53]
Total Volume (V )=V C +2V H …… (4.3)
Volume of hemispherical head can be calculated by this formula,

2 2
V H = π R 3= π D 3
3 24
D
∴ R=
2
2
V H= × 3.14 ×¿
24
Total Volume ( V ) =2.4939+2 ( 0.3465 )=3.1867 m 3=3186.7 L=841.64 Gallons

4.1.6) Thickness of Reactor: (tc)
Thickness of reactor depends upon the material of construction of the reactor. While material of
construction can be selected according to internal pressure of the reactor. As the reactor’s
internal pressure is 400 KPa, we select the stainless steel (SS-316) which has a greater ability to
bear more pressure and due to safety concerns. [53]
Operating Pressure = P = 400 KPa

Working Stress of the material = S = 79300 KPa at 100℃
Joint Efficiency = Ej = 0.85
Corrosion allowance = Cc = 0.0003 m = 0.3 mm
Internal Radius of Shell = R = D/2 = 0.549 m = 549 mm
We know that,
P×R
t c= +C c
( S × E j)−0.6 P
We can calculate thickness for this formula,

400 × 0.549
t c= +0.0003=0.00357 m=3.569 mm
(79300 × 0.85 )−(0.6 × 400)
61
4.1.7) Jacketed Area: (Aj)

According to the Table 7.3 (Chemical Process Engineering Design and Economics by H. Silla)
the Jacketed Area from this capacity of reactor will be 79 ft2, which is equals to 7.3391 m2. [53]
Now, we will calculated the required area for the required heat transfer in reactor.
The required heat rate in the reactor (according to energy balance) Qr = 48267.27 KJ/h
Avg. Steam temperature for heat transfer (Tjavg. = (180+110)/2 = 145 ℃
Temperature of Reactor TR = 80 ℃
Heat transfer coefficient (Table 7.4 by H. Silla) Ud = 1737.46 KJ/h.m2.℃
Now,
Q r =U d A j ( T javg. −T R )
Qr 48267.27 2
A j= = =0.4273 m
U d ( T javg . −T R ) 1737.46× 145−80
( )
While our available jacketed area is much much greater than required. Hence Jacked Area is
sufficient for required heat transfer.
4.1.8) Weight of Reactor: (Wr)

To calculate weight of the reactor has much importance with respect to construction and cost
estimation of the reactor. [53]
Weight of Cylinder/Heads = Surface Area × Density of Material × Thickness
Surface Area=2 πrL+ 2 π r 2=10.98 m2

Weight of Cylinder = 10.98 × 7880 × 0.00357 = 308.97 Kg
Surface Area of Heads=2× ( 2× π r 2) =3.78 m 2

Weight of Heads = 3.78 × 7880 × 0.0019 = 57.60 Kg
Weight of Fluids = 501.84 Kg/h × 4 h = 2007 Kg
Total Weight = Weight of Cylinder + Weight of Heads + Weight of Fluids

Wr = 308.97 + 57.60 + 2007 = 2373 Kg
62
4.1.9) Power Required: (P)

According to the Table 7.7 (Chemical Process Engineering Design and Economics by H. Silla)
the power factor per unit volume for Liquid Reactions with Heat Transfer is 689.5 W/m3. [53]
P= p V c =689.5 × 2.4939=1719.5 W =1.719 KW
4.1.10) Mechanical Design of Reactor:

The Proper dimension wise mechanical design of reactor is given blow in different Figures.
Fig 4.2
(General
Design of
CSTR)
Fig 4.3
(Design
Specifications of CSTR)
63
Top View of CSTR is shown below in Fig 4.4

4.1.11) Specification Sheet of Reactor:
Item: Reactor
Item No. R-1
No. Required: 1
Type: Jacketed CSTR (Continuous Stirrer Tank Reactor)
Volume: 3.18 m3
Height: 2.635 m
Diameter: 1.098 m
Height to Diameter Ratio: 2.4 m
Type of Head: Hemispherical
Wall Thickness: 0.00357 m
Material of Construction: Stainless Steel (SS-316)
64
4.2) Design of Distillation Column:
In industry it is common practice to separate a liquid mixture by distilling the components, which
have lower boiling points when they are in pure condition from those having higher boiling points.
This process is accomplished by partial vaporization and subsequent condensation.
4.2.1) Distillation is defined as:

“Process in which a liquid or vapor mixture of two or more substances is separated into its
component fractions of desired purity, by the
application and removal of heat.”
65
Fig. 4.5 (Phenomenon of Distillation)
4.2.2) Types of Distillation Columns:

There are many types of distillation columns, each designed to perform specific types of
separations, and each design differs in terms of complexity.
 Batch columns
 Continuous columns
Batch Columns:
In batch operation, the feed to the column is introduced batch-wise. That is, the column is
charged with a 'batch' and then the distillation process is carried out. When the desired task is
achieved, a next batch of feed is introduced.
Continuous Columns:
In contrast, continuous columns process a continuous feed stream. No interruptions occur unless
there is a problem with the column or surrounding process units. They are capable of handling
high throughputs and are the more common of the two types. We shall concentrate only on this
class of columns.
4.2.3) Choice between Plate and Packed Column:
Vapor liquid mass transfer operation may be carried either in plate or packed column. These two
types of operation are quite different. The relative merits of plate over packed column are as
follows:
1. Plate column are designed to handle wide range of liquid flow rates without flooding.
2. If a system contains solid contents; it will be handled in plate column, because solid will
accumulate in the voids, coating the packing materials and making it ineffective.
3. Dispersion difficulties are handled in plate column when flow rate of liquid are low as
compared to gases.
66
4. For large column heights, weight of the packed column is more than plate column.
5. If periodic cleaning is required, man holes will be provided for cleaning. In packed
columns packing must be removed before cleaning.
6. For non-foaming systems the plate column is preferred.
7. Design information for plate column is more readily available and more reliable than that
for packed column.
8. Inter stage cooling can be provided to remove heat of reaction or solution in plate
column.
9. When temperature change is involved, packing may be damaged.
We’ve selected plate column because:
1. System is non-foaming.
2. Temperature is high i.e. 80℃.
Choice of Plate Type:
There are three main types, sieve tray, bubble cap, valve tray. I’ve selected sieve tray because:
1. They are lighter in weight and less expensive. It is easier and cheaper to install.
2. Pressure drop is low as compared to bubble cap trays.
3. Peak efficiency is generally high.
4. Maintenance cost is reduced due to the ease of cleaning.
Selection Criteria of Trays
 Cost
Cost of plate depends upon material of construction used.
For mild steel, the ratio of cost between plates is
Sieve plate : valve plate : bubble-cap plate
3 : 1.5 : 1.0
 Capacity:
Sieve tray > valve tray > bubble-cap tray
 Operating Range:
It is the range of liquid and vapor flow rates which must be above the weeping conditions and
below the flooding conditions. Operating range flexibility comparison is
Bubble cape tray > Valve tray > Sieve tray
For good design, sieve plate gives satisfactory operating range.
67
 Pressure drop
Bubble-cap tray > valve tray > sieve tray
Choice of Tray Type (Sieve Tray)
 Sieve plates are lighter in weight and less expensive. It is easier and cheaper to install.
 Pressure drop is low as compared to bubble cap trays.
 Maintenance cost is reduced due to ease of cleaning.
 If properly designed, sieve tray gives desired separation
Fig 4.6 (Sieve Trays in Distillation Column)

4.2.4) Main Components of Distillation Columns:
Column internals such as trays/plates and/or packing which are used to enhance component
separations.
 A reboiler to provide the necessary vaporization for the distillation process. The liquid
removed from the reboiler is known as the bottoms product or simply, bottoms.
 A condenser to cool and condense the vapor leaving the top of the column. The
condensed liquid that is removed from the system is known as the distillate or top
product.
 A reflux drums to hold the condensed vapor from the top of the column so that liquid
(reflux) can be recycled back to the column. The condensed liquid is stored in a holding
vessel known as the reflux drum. Some of this liquid is recycled back to the top of the
column and this is called the reflux.
68
Fig 4.7 (A schematic of a typical distillation unit with a single feed and two
product streams is shown above.)
4.2.5) Factors affecting Distillation Column Operation:

Vapor Flow Conditions
Adverse vapor flow conditions can cause:
 Foaming
 Entrainment
 Weeping/dumping
 Flooding
Foaming:
Foaming refers to the expansion of liquid due to passage of vapor or gas. Although it provides
high interfacial liquid-vapor contact, excessive foaming often leads to liquid buildup on trays. In
some cases, foaming may be so bad that the foam mixes with liquid on the tray above. Whether
foaming will occur depends primarily on physical properties of the liquid mixtures, but is
sometimes due to tray designs and condition. Whatever the cause, separation efficiency is always
reduced.
69
Entrainment:
Entrainment refers to the liquid carried by vapor up to the tray above and is again caused by high
vapor flow rates. It is detrimental because tray efficiency is reduced: lower volatile material is
carried to a plate holding liquid of higher volatility. It could also contaminate high purity
distillate. Excessive entrainment can lead to flooding.
Weeping/Dumping:
This phenomenon is caused by low vapor flow. The pressure exerted by the vapor is insufficient
to hold up the liquid on the tray. Therefore, liquid starts to leak through perforations. Excessive
weeping will lead to dumping. That is the liquid on all trays will crash (dump) through to the
base of the column (via a domino effect) and the column will have to be re-started. Weeping is
indicated by a sharp pressure drop in the column and reduced separation efficiency.
Flooding:
Flooding is brought about by excessive vapor flow, causing liquid to be entrained in the vapor up
the column. The increased pressure from excessive vapor also backs up the liquid in the down
comer, causing an increase in liquid holdup on the plate above. Depending on the degree of
flooding, the maximum capacity of the column may be severely reduced. Flooding is detected by
sharp increases in column differential pressure and significant decrease in separation efficiency.
Reflux Conditions:
Minimum trays are required under total reflux conditions, i.e. there is no withdrawal of distillate.
On the other hand, as reflux is decreased, more and more trays are required.
Feed Conditions:
The state of the feed mixture and feed composition affects the operating lines and hence the
number of stages required for separation. It also affects the location of feed tray.
State of Trays and Packing’s:
Remember that the actual number of trays required for a particular separation duty is determined
by the efficiency of the plate. Thus, any factors that cause a decrease in tray efficiency will also
change the performance of the column. Tray efficiencies are affected by fouling, wear and tear
and corrosion, and the rates at which these occur depends on the properties of the liquids being
processed. Thus appropriate materials should be specified for tray construction.
Column Diameter:
Vapor flow velocity is dependent on column diameter. Weeping determines the minimum vapor
flow required while flooding determines the maximum vapor flow allowed, hence column
capacity. Thus, if the column diameter is not sized properly, the column will not perform well.
70
4.2.5) Design Steps and Calculation for Distillation Column:

Design Steps of Distillation Colum:
 Calculation of minimum reflux ratio rm

 Calculation of actual reflux ratio
 Calculation of theoretical number of stage
 Calculation of actual number of stages
 Calculation of diameter of the column
 Calculation of flooding point
 Calculation of pressure drop
 Calculation of the height of the column
Where,
X = fraction of more volatile component in feed distillate and waste respectively
Xf = 0.2848
Xd = 0.99
Xw = 0.001
Nature of feed:
xi = mole fraction in liquid phase, yi = mole fraction in gas phase
And we enter the feed at the boiling point of light component which is methanol so we enter the
feed at 80°C.
Relative Volatility: ∝ = (Pa°)/ (Pb°) = 8
Calculation of minimum reflux ratio:

Ya = αXa / (1+ (α-1) Xa)
Solving for Yf
Where Xf = 0.2848
Ya = 8 x 0.591/(1+(8-1)0.591)
Where Yf = 0.76
Now for minimum reflux ratio:
71
Rm = ((Xd - Yf))/ ((Yf - Xf))

Rm = (0.999-0.76) / (0.76-0.2848)
Rm = 0.503
We take reflux as 1.3 times the minimum:
R = 1.3 × Rm
R = 0.6
From minimum reflux ratio
R= Ln/D
So, Ln = 394.2 Kmol/h
And we know that,
Vn = L n + D
Vn = 1000 Kg/h
Similarly for stripping section as we enter the feed at its boiling point so,
Lm = Ln + F
Lm = 2523.2 Kg/h
From plate balance we know,

Lm = Vm + W Vm = 1916 Kg/h
Theoretical number of Stages:

From equation 11.58 (page 524) Coulson vol#06
Nm = (ln (xA / xB) d(xB /xA)B)/ln ⁡ 〖 (∝AB)avg 〗

So,
Nm = (ln (0.99/0.01)d (0.9/0.01)B)/ ln (81)
We get, Minimum no plates = Nm = 4 plates
Theoretical number of plates:
72
Gilliland related the number of equilibrium stages and the minimum reflux ratio and the
no. of equilibrium stages with a plot that was transformed by Eduljee into the relation:
(N - Nmin) / (N+1) = 0.75 [1 – (R - Rmin /(R+1)] 0.566]
By putting values,
(N - 2)/ (N+1) = 0.75 [1 – ((0.6-0.503)/1.6 ] 0.566]
So,
N = 7 Plates
Location of feed plates:
We use Kirkbride’s method for finding feed point location.
(Equation 11.62 Coulson vol#06)
Log [ND /NB ] = 0.206 log[(B/D) (xLk/xHk) F {(xLk)B /((xHk) D) B }2] B and D are bottom
and distillate respectively
log [ND /NB ] = 0.206log[(606.524/606.524)(0.66/0.2848 ) {0.98 /0.002 }2]
log [ND /NB ] = 0.6895
So
ND = 0.6238 NB
And we know that
ND + NB = 7
So,
ND = 3.8 & NB = 3.2
So feed will be at 3rd plate from the bottom
Calculation of actual number of stages:
For finding Column efficiency (ε) we need viscosity so for finding viscosity.
Average temperature of column = 80 ℃

Feed viscosity at average column temperature = µavg = 0.033 Ns/m²
Relative volatility = αavg = 28
So efficiency is calculated by O'Connell's correlation formula
(Equation 11.67 Coulson vol # 06)
73
Efficiency = ε = 51-32.5 [log (µavg αavg)] = 51 – 32.5 [log (0.033) (28)]

ε = 82%
Number of actual trays = 7/0.82 = 9 Plates
Calculation of column diameter:
Vapor load at bottom = Qv = Vm /ρv
Vm = maximum flow rate in stripping section = 1916 Kg/h
ρv = density of vapour = 850 Kg/m³
Avg molecular weight of vapour = 60 Kg/Kmol
So, Qv = (1916× 60) / (850 × 3600)
And Qv = 0.037 m3 /s
And liquid load at the bottom = QL = Lm /ρL
Lm = liquid return = 2523 Kg /h
ρL = density of liquid = 850 Kg/m³
Avg. molecular weight at bottom = 60 Kg/Kmol
So, QL = (533.489 × 55.46) / (850 × 3600)
And, QL = 0.042 m3 /s
Tray Dynamics:
FLv = (Lm /Vm) (ρv/ρL ) 0.5
= (2523/1916) (0.196/0.196) 0.5
= 0.02189
Capacity Parameter:
Assumed tray spacing = 700 mm = 0.7
Surface tension of system = σ = 42.2 dynes/cm Csb is finding by graph b/w Flv and tray spacing.
Souder's brown coefficient = Csb = 0.1048 m/s
Net Vapor Velocity at Flooding:
We find the flooding velocity be following formula
Vnf = Csb (σ/20) 0.2 [ ((ρl - ρv)/ρv)]
74
By putting values we get, Vnf = 5.87 m/s

Actual Vapor Velocity:
We assume that our plant is operating at 80% of flooding velocity
VA = 0.80 Vnf = 0.80 × 2.3685 m/s
VA = 4.7 m/s
Net-Area
AN = Volumetric flow rate of vapor
Actual vapor velocity
Volumetric flow rate of vapours = 10 Kg/h
AN = 2.12 m2
Assume that down comer occupies 15% of Cross-sectional Area; then
Cross-Sectional Area:
AC = 2.12/0.85
Ac = 2.49 m2
Diameter of Column:
Since we have
Ac = π/4 D2
By rearranging we get
D = √ ((4 *Ac)/π)
Know by putting values.
D = √ ((4 *2.49)/3.14)
D = 1.8 m
Calculation of Flooding Point:
Vn = Qv /an = 0.037/2.12 = 0.0174 m/s
Net Area:
Net area = An =1.687 m2
And we know that
75
Active area = Aa = Ac - 2Ad

Down-comer area = Ad = 0.15 Ac
Ad = 0.15 × 2.49 = 0.3735 m2
Now, Aa = Ac - 2Ad = 2.49 – 2 (0.3735) = 1.74 m2
Hole Area:
We know that hole area is 10 % of active area so, Ah = 0.1 Aa = 0.1762 m2
Assume
Weir height = hw = 25 mm = 0.025 m
Hole diameter = dh = 5 mm = 0.005 m
Plate thickness = xw = 5 mm = 0.005 m
Assume,
Pressure drop = 0.67 KPa /per tray
Pressure Drop over the Entire Column
So pressure drop in the column is
∆PT = 0.67 × 10
∆PT = 6.7 KPa
Height of Distillation Column:
Height of column Hc = (Nact-1) Hs + ∆H + Plates thickness
Nact = No. of plates = 9
Hs = Tray spacing = 0.7 m
Distance between 10 plates = 0.7 × (10-1) = 6.3 m
Top clearance = 700 mm = 0.7 m
Bottom clearance = 700 mm = 0.7 m
∆H = disengagement height = top clearance + bottom clearance = (0.7 + 0.7) = 1.4 m
Tray thickness = 0.005 m/plate
Total thickness of trays = 0.005 × 10 = 0.05 m
So, Total Height = 6.3 + 1.4 + 0.05 = 8 m
76
Specification Sheet:
• Minimum Reflux Ratio = 0.503
• Theoretical Number of Plates = 7
• Actual Number of Plates = 9
• Cross sectional Area = 2.29 m2
• Net Area = 2.49 m2
• Diameter of column = 1.8m
• Height of column = 6 m
4.3) Heat Exchanger Design

A heat exchanger is a heat-transfer devise that is used for transfer of internal thermal energy
between two or more fluids available at different temperatures. In most heat exchangers, the
fluids are separated by a heat-transfer surface, and ideally they do not mix. Heat exchangers are
used in the process, power, petroleum, transportation, air conditioning, refrigeration, cryogenic,
heat recovery, alternate fuels, and other industries. Common examples of heat exchangers
familiar to us in day-to-day use are automobile radiators, condensers, evaporators, air pre-
heaters, and oil cooler.
77
4.3.1) Heat Exchanger Terms:

Heat exchanger: both sides single-phase and process streams
Cooler: one stream a process fluid and the other cooling water or air.
Heater: one stream a process fluid and the other a hot utility, such as steam or hot oil.
Condenser: one stream a condensing vapor and the other cooling water or air.
Chiller: one stream a process fluid being condensed at sub-atmospheric temperatures and the
other a boiling refrigerant or process stream.
Reboiler: one stream a bottoms stream from a distillation column and the other a hot utility
(steam or hot oil) or a process stream.
Table 4.4 (Selection Guide to Heat Exchanger Types)
Approximat
e relative
Type Significant feature Applications best suited Limitations cost in
carbon steel
construction
Condensers; liquid-liquid; Temperature difference
Fixed tube Both tube sheets gas-gas; gas-liquid; cooling at extremes of about
o 1.0
sheet fixed to shell. and heating, horizontal or 200 f Due to
vertical, reboiling. differential expansion.
One tube sheet
Floating “floats” in shell or
High temperature Internal gaskets offer
head or tube with shell, tube
differentials, above about danger of leaking.
sheet bundle may or may
200 of extremes; dirty fluids Corrosiveness of fluids
(removable not be removable 1.28
requiring cleaning of inside on shell-side floating
and non- from shell, but back
as well as outside of shell, parts. Usually confined
removable cover can be
horizontal or vertical. to horizontal units.
bundles) removed to expose
tube ends.
U-tube; Only one tube sheet High temperature Bends must be 0.9-1.1
required. Tubes differentials, which might carefully made, or
U-Bundle
bent in U-shape. require provision for mechanical damage
Bundle is expansion in fixed tube and danger of rupture
removable. units. Easily cleaned can result. Tube side
conditions on both tube and velocities can cause
78
erosion of inside of
bends. Fluid should be
shell side.
free of suspended
particles.
Each tube has own
Relatively small transfer
shell forming
area service, or in banks for Services suitable for
annular space for
larger applications. finned tube. Piping-up
Double pipe shell side fluid. 0.8-1.4
Especially suited for high a large number often
Usually use
pressures in tube (greater requires cost and space.
externally finned
than 400 psig).
tube.
Pipe coil for
submersion in coil- Transfer coefficient is
Condensing, or relatively
box of water or low, requires relatively
Pipe coil low heat loads on sensible 0.5-0.7
sprayed with water large space if heat load
transfer.
is simplest type of is high.
exchanger.
Not well suited for
Composed of
boiling or condensing;
metal-formed thin Viscous fluids, corrosive
Plate and limit 350-500 of by
plates separated by fluids, slurries, high heat 0.8-1.5
frame gaskets. Used for
gaskets. Compact, transfer.
liquid-liquid only; not
easy to clean.
gas-gas.
Compact,
concentric plates; Cross-flow, condensing, Process corrosion,
Spiral 0.8-1.5
no bypassing, high heating. suspended materials.
turbulence.
4.3.2) Shell and Tube Heat Exchanger:

In process industries, shell and tube exchangers are used in great numbers, far more than any
other type of exchanger. More than 90% of heat exchangers used in industry are of the shell and
tube type. The shell and tube heat exchangers are the “work horses” of industrial process heat
transfer. They are the first choice because of well-established procedures for design and
manufacture from a wide variety of materials, many years of satisfactory service, and availability
of codes and standards for design and fabrication. They are produced in the widest variety of
sizes and styles. There is virtually no limit on the operating temperature and pressure.
4.3.3) Selection Criterion for heat exchangers:
79
 Material of construction
 Operating temperatures and pressures, temperature program and temperature driving
forces
 Flow rates
 Flow arrangements
 Performance parameters (thermal effectiveness and pressure drops)
 Fouling tendencies
 Types and phases of fluid
 Maintenance, inspection, cleaning ,extension and repair possibilities
 Overall economy
 Fabrication techniques
Material of construction:
For reliable and continuous use, the material of construction of heat exchangers should have well
defined corrosion rate in service environment. Furthermore, the material should exhibit strength
to with stand with operating temperature and pressure.
Operating temperature and pressure:

Pressure:
The design pressure is important to determine the thickness of pressure retaining components.
The higher the pressure, the greater will be required thickness of pressure retaining membrane.
Temperature:
Design temperature: This parameter is important as it indicate whether a material at design
temperature can withstand the operating pressure and various load imposed on component.
Shell and tube heat exchanger units can be designed for almost all condition of temperature and
pressure. In extreme cases, high pressure may impose a limitation by fabrication problems
associate with material thickness.
Flow rate:
Flow rate determine the flow area: the higher the flow rate the higher will be cross flow area.
Flow arrangement
The choice of typical flow arrangement is dependent of required exchanger effectiveness,
exchanger construction types.
80
Performance Parameters:
Thermal effectiveness:
For high performance service requiring high thermal effectiveness, use blazed plate-fin
exchanger. Use tube fin exchanger for slightly less thermal effectiveness and use shell and tube
for low-thermal effectiveness
Pressure drop:
Pressure drop is an important parameter in heat exchanger design. The heat exchanger should be
design in such a way that unproductive pressure drop should be avoided to maximum extent in
area like inlet and outlet bends, nozzles and manifolds.
Fouling Tendencies:
Fouling is defined as formation on heat exchanger surface of undesirable deposit that decrease
the heat transfer and increase the resistance to fluid flow, resulting in high pressure drop. The
growth of those deposit decrease the performance of exchanger with time.
Type and Phases of fluid:
The phase of fluid within the unit is an important consideration in selection of heat exchanger
type. Various combination of fluid dealt in exchanger are Liquid-Liquid, Liquid-Gas and Gas-
Gas.
Maintenance, inspection, cleaning, extension and repair possibilities.
The suitability of various heat exchanger depend upon it maintenance cleaning and repairing
Maintenance and repair of some of shell and tube exchanger is possible but repair of expansion
joint is difficult.
Tubes can be renew and plugged. Repair of compact heat exchanger of tube fin type is very
difficult except by plugging of tube. Repair of plate fin exchanger is very difficult.
Overall Economy:
There are two major cost to consider in designing of heat exchanger, the manufacturing cost and
operating cost, including maintenance cost. In general the les heat transfer area the less is
complexity of design, the lower in manufacturing cost. The operating cost is pumping cost due to
pumping device such as pumps, fans and blowers. The maintenance cost include cost of spares
that require frequent renewal due to fouling and corrosion.
Fabrication technique:
81
Fabrication technique is also determining factor for heat exchanger design. For example shell
and tube exchanger mostly fabricated by welding, plate fin heat exchanger and automobile
aluminum radiator by brazing. Most of circular tube fin exchanger fabricate by mechanical
assembling.
Classification of Heat Exchangers:
Heat exchangers have been developed with different approaches to these four
fundamental design factors. Three principal types of heat exchangers
 Fixed tube-sheet exchangers
 U-tube exchangers and
 Floating head exchangers
Essentially, a shell and tube exchanger consists of a bundle of tubes enclosed in a cylindrical
shell. The ends of the tubes are fitted into tube sheets, which separate the shell-side and tube-side
fluids. Baffles are provided in the shell to direct the fluid flow and support the tubes. The
assembly of baffles and tubes is held together by support rods and spacers,
The simplest and cheapest type of shell and tube exchanger is the fixed tube sheet design.
The main disadvantages of this type are that the tube bundle cannot be removed for cleaning and
there is no provision for differential expansion of the shell and tubes.
As the shell and tubes will be at different temperatures, and may be of different materials, the
differential expansion can be considerable and the use of this type is limited to temperature
differences up to about 80°C. Some provision for expansion can be made by including an
expansion loop in the shell but their use is limited to low shell pressure; up to about 8 bar.
In the other types, only one end of the tubes is fixed and the bundle can expand freely
The U-tube (U-bundle) type requires only one tube sheet and is cheaper than the floating-head
types;
But is limited in use to relatively clean fluids as the tubes and bundle are difficult to clean. It is
also more difficult to replace a tube in this type.
Exchangers with an internal floating head, are more versatile than fixed head and U-tube
exchangers.
They are suitable for high-temperature differentials and, as the tubes can be rodded from end to
end and the bundle removed, are easier to clean and can be used for fouling liquids.
A disadvantage of the pull-through design, is that the clearance between the outermost tubes in
the bundle and the shell must be made greater than in the fixed and U-tube designs to
accommodate the floating head flange, allowing fluid to bypass the tubes.
82
The clamp ring (split flange design), is used to reduce the clearance needed. There will always be
a danger of leakage occurring from the internal flanges in these floating head designs.
Fluid allocation:
Shell or tubes; where no phase change occurs, the following factors will determine the allocation
of the Fluid streams to the shell or tubes.
Corrosion:
The more corrosive fluid should be allocated to the tube-side. This will reduce the cost of
expensive alloy or clad components.
Fouling:
The fluid that has the greatest tendency to foul the heat-transfer surfaces should be
Placed in the tubes. This will give better control over the design fluid velocity, and the higher
Allowable velocity in the tubes will reduce fouling. Also, the tubes will be easier to clean.
Fluid temperatures:
If the temperatures are high enough to require the use of special alloys placing the higher
temperature fluid in the tubes will reduce the overall cost. At Moderate temperatures, placing
hotter fluid in the tubes will reduce the shell surface Temperatures, and hence the need for
lagging to reduce heat loss, or for safety reasons.
Operating pressures:
The higher pressure stream should be allocated to the tube-side. High-pressure tubes will be
cheaper than a high-pressure shell.
Pressure drop: For the same pressure drop, higher heat-transfer coefficients will be obtained on
the tube-side than the shell-side, and fluid with the lowest allowable pressure drop should be
allocated to the tube-side.
Viscosity:
Generally, a higher heat-transfer coefficient will be obtained by allocating the more viscous
material to the shell-side, providing the flow is turbulent.
Stream flow-rates:
Allocating the fluids with the lowest flow-rate to the shell-side will normally give the most
economical design.
4.3.4) Design Procedure for Shell and Tube Heat Exchanger:
83
Table 4.5 (Design procedure for shell-and-tube heat exchangers)

Design Steps:
Step # 1
General heat transfer equation across a surface
Heat Duty
Q = m*Cp*∆Tlm
= 10537.26KJ/h
84
Mass Flow rate

M = Q/Cp ∆T = 185.83 Kg/h
Volumetric Flow rate:
Q = Cp ∆T/Q = 670.23 m3
Step # 2
Physical Properties of Cold Stream:
Properties: Values:
Mass Flow Rate mc 184.696 Kg/h
Entering Temperature t1 25oc
Leaving Temperature t2 38.5oc
Specific Heat Capacity Cpc 4.226 KJ/Kg oC
Viscosity Of water µc 0.79×10-2 Kg/m.s
Thermal Conductivity kc 0.358 W/m.K
Density ρc 998 Kg/m3
Physical Properties of Hot Stream:

Mass Flow Rate 184.69 Kg/h
Entering Temperature t1 150oC
Leaving Temperature t2 136.5oC
Specific Heat Capacity Cp 4.2 KJ/Kg oC
Viscosity µ 0.079×10-2 Kg/m.s
Thermal Conductivity k 0.0358 W/m.K
Density ρ 0.551 Kg/m3
Step # 3
Assume the value of Overall heat transfer Coefficient Uassumed
85
Using Table (Coulson Volume 6)

U assumed = 2500 W/m2 oC
Step # 4
Calculation of LMTD
(T 1−t 2)−(T 2 −t 1 )
∆ T lm=
(T −t )
ln 1 2
(T 2−t 1)
∆Tlm= log mean temperature difference

T1= hot inlet temperature
T2= hot outlet temperature
t1= cold inlet temperature
t2= cold outlet temperature
∆Tlm= 124.80 oC
∆ T m=F t × ∆ T lm
∆Tm = Mean temperature difference

Ft = Temperature Correction Factor
∆Tlm= log mean temperature difference
The correction factor is a function of the shell and tube fluid temperatures, and the number of
tube and shell passes. It is normally correlated as a function of two dimensionless temperature
ratios.
(T 1−T 2 ) (t −t )
R= , S= 2 1
(t 2−t 1 ) (T 1−t 1)
R is equal to the shell-side fluid flow-rate times the fluid mean specific heat; divided by the tube-
side fluid flow-rate times the tube-side fluid specific heat. S is a measure of the temperature
efficiency of the exchanger. So,
R=1
S = 0.108
86
Ft can be calculated by putting the values of R & S

Ft = 0.901
∆Tm = 112.31 oC
Assumptions:
The following assumptions are made in the derivation of the temperature correction
Factor Ft, in addition to those made for the calculation of the log mean temperature
Difference:
 Equal heat transfer areas in each pass.
 A constant overall heat-transfer coefficient in each pass.
 The temperature of the shell-side fluid in any pass is constant across any cross- section.
 There is no leakage of fluid between shell passes.
Though these conditions will not be strictly satisfied in practical heat exchangers, the Ft values
obtained from the curves will give an estimate of the “true mean temperature difference” that is
sufficiently accurate for most designs.
Step # 5
Determine the heat transfer area required
Q = Uassumed AT ∆Tm
Q = Rate of Heat transfer, (KJ/h)
Uassumed = Assumed value of overall heat transfer coefficient, (W/m2 °C)
AT = Heat Transfer area (m2)
∆Tm = Mean Temperature Difference (°C)
AT = Q / ∆Tm Uassumed
AT = 373.39 m2
Step # 6
87
Tube side Fluid is water

Shell side fluid is steam
Do = tubes outside diameter = 0.05 m
Di = tube inside diameter = 0.024 m
L = tube length = 4.88 m
Area of tube
At = π do L = 0.766 m2
Step # 7
Calculate the Total number of tubes
Nt = No of tubes
Nt = Total heat transfer Area/ Area of a tube =AT/At = 487.35
Step # 8
Calculate Shell Diameter Ds
Shell Diameter Ds = Db + bundle clearance
Db = Bundle diameter, mm
Db =d o × ¿
Nt = No. of Tubes
Db = Bundle diameter (mm)
Do = tubes outside diameter (mm)
As we use the triangular and rotated square patterns so,
K1 = 0.175, n1= 2.285
Db= 230 mm
Use split -ring floating head type exchanger
Bundle diameter clearance= 52mm
Ds = 230 + 53 = 280 mm = 0.280 m
88
Step # 9
Calculate tube side coefficient
1/3
k Cp μ
hi = j h ( )
De k
Re= ρvdi/ = 1.4×104
Pr= Cp /k = 0.46
Jh= 3.9×10-3
hi = 3520 (W/m2 oC)
Step # 10
Calculate shell side coefficient
1
H S DE
=J H ℜ Pr 3 ¿
KF
Re= ρvdi/ = 8.5×104

Pr= Cp /k = 7.08
Hs = 6453.6 (W/m2oC)
Step # 11
Calculate overall heat transfer coefficient
1 1 1
Doln ( DoDi ) +1/ Hi Do + 1 Do
= +
U 0 H 0 H Od
+
2K W
( Di ) H ( Di )
Id ❑
Uo= 2700 (W/m2 oC) which is close to assumed value, which is acceptable.
Step # 12
89
Calculate Tube side pressure drop

∆ Pt =Np ¿
= 2996.176 pa =2.96 KPa

Step # 13
Calculate shell side pressure drop
ΡV2 −0.14
Ds L Μ
∆Ps = 8 jf ( )( )( )( )
De Lb 2 ΜW
= 1123 pa = 1.12 KPa

All quantities in equations are already known except jf , which can be calculated from graph.
Neglect ¿ For non-viscous fluids.
4.4) Evaporator Design:

Evaporation, a widely used method for the concentration of aqueous solutions, involves
the removal of water from a solution by boiling the liquor in a suitable vessel, an
evaporator, and withdrawing the vapors. If solutions contain dissolved solids, resulting
strong Liquor may become saturated so that crystals are deposited.
90
The selection of the evaporators depends upon the following factors:
 High product viscosity.

 Heat sensitivity.
 Scale formation and deposition.
 The properties of the liquid to be evaporated
 Capital and running costs
 Capacity
 Holdup
 Residence time
4.4.1) Types of Evaporator:

Evaporators may be divided into three main types:
 Natural circulation units.

 Forced circulation units.
 Film-type units.
4.4.2) Forced Circulation Evaporator:

This type of evaporators is used in that industry where continues flow of high viscous fluid is
required. If the velocity of liquor through tubes Increasing, results in a significant increase in the
liquid-film transfer coefficient. This is achieved in the forced circulation units where a propeller
or other impeller is mounted in the central down comer, or a circulating pump is mounted
outside the evaporator body. Forced circulation enables higher degrees of concentration to
be achieved, since the heat transfer rate can be maintained in spite of the increased viscosity
of the liquid. Some common types of vaporizers are
 Vertical vaporizer
 Indirect fluid heater
 Tubular low temperature vaporizer
 Electrical resistance vaporizer
 Cryogenic vaporizer
The commonest type of vaporizer is the ordinary horizontal 1-2 exchanger or one of its
modifications, and vaporization may occur in the shell or in the tubes. If steam is the heating
medium, the corrosive action of air in the hot condensate usually makes it advantageous to carry
out the vaporization in the shell.
In the case of vaporizer, however, operation is often at high pressure, and it is usually too
expensive to provide disengagement space in the shell, since the inclusion of disengagement
91
space at high pressures correspondingly increases the shell thickness. For this reason vaporizers
are not usually designed for internal disengagement. Instead some external means. Such as an
inexpensive welded drum, is connected to the vaporizer where in the entrained liquid is separated
from the vapor.
4.4.3) Design Calculation Steps:
190oC 115oC
110oC 55oC
Composition:
FAME = 348.86 Kg/h

Water = 88.98 Kg/h
Heat Duty:
Q˙ 1∨Q̇ 2=ṁ ¿
To calculate heat duty this formula is used for Methanol and water.
Q˙ 1=88.98 ¿
Q˙ 1=219412.5 KJ / h
In the same Q˙ 2=715.19 KJ / h
And for Q̇ 3=mCp ∆ T
Q˙ 3=49788.2 KJ /h
Q=¿ Q˙ 1+˙Q˙ 2+ Q3
˙ ¿
˙
Q=269915.8 KJ /h
Steam Required:
92
Q=mCp
˙ ∆T
Q/∆ TCp=m
m = 1730.2Kg/h
LMTD:
For Preheating:
( 190−110 )−( 115−55 )

LMTD=
190−110
ln (
115−55 ) = 69.68 ᵒC
T 1−T 2
R= =1 . 36
t 1−t 2
t 2 −t 1
S= =0 . 407
T 1−t 1
Ft=0.868
Tm=60.48 ᵒC
Let assume
Ud = 50 KJ/h.m2.ᵒC
Q=UAT m
Q
A=
UT m
A= 89.25 m2
Tube Lay out & size:
Inner diameter of tube = 16 mm
Outer diameter of tube = 20 mm
L = 4.88 m
Area of the one tube = π × do × l
Area of one tube = 0.303 m
93
Numbers of tubes =area/area of one tube = 294

Tube Cross-Sectional Area = π/4di2
Total flow area = no. of tubes per pass × cross-sectional area
Total flow area = (148*(0.016)2*3.14)/4
Total flow area = 0.0297 m2
Linear velocity = flow rate/Total flow area and density of mixture.
Linear velocity = v = 27.4 m/s
Calculation for Re & Pr

Re = (0.59×27.4×16×10-3)/0.000012
Re = 21240
Pr = (2.08*0.000012)/(0.0427)
Pr = 96
L 4.83
= =302
D 16 ×10−3
Jh = 3.9×10-2
(Taking the value of Reynolds number from a graph at Richardson & Coulson at the Page # 522
Volume 1)
1/3
k Cp μ
hi = jh ( )
di k
hi = 66.874 KJ/h.m2.ᵒC
Cold fluid (Shell Side):

For triangular pitch, two pass.
k1=0.249, n1 = 2.207 (Constants)
Db =d o × ¿
Db = 0.4932 m
Bundle clearance = 13 mm
94
Shell diameter = Ds = Bundle diameter + Bundle clearance

Shell diameter= 0.5062 m
Tube pitch
Pt = 1.25×do
Pt = 0.025 m
Baffle height or cut 25% of Ds = 0.25×0.506 = 0.1265
Baffle height = 0.506 - 0.1265 = 0.379 m
Baffle spacing = 0.66×0.5062
B = 0.3340 m
Tolerance = Pt - do
Pd = 0.005 m
Shell side flow area:

Flow Area As = (Pd × B × Ds) / Pt
Flow area = 0.03382 m2
Mass velocity = 438.433/0.03382 = 12963.7 Kg/h.m2
Hydraulic diameter
Dh = 1.316 m
Shell side Re & Pr:

Re = 3293485.5
Pr = 0.0081
Jh = 7*10-3 (By using table from Coulson Volume 6)
1/3
k Cp μ
ho = j h ( )
De k
ho = 659 KJ/h.m2 ᵒC
95
Overall heat transfer co-efficent:

1/Uo = (1/hi + 1/hio) do/di + doln (do/di)/ 2kw + 1/ho + 1/hod
1/Uo=0.0192
Uo = 52.08 KJ/h.m2.ᵒC
This value is close to assumed value.
4.4.4) Pressure Drop:

Tube Side:
The pressure drop on tube side calculated as;
∆P = Np [8jf (L/di) + 2.5]ϼut2 / 2
Np = 2
L = 4.83 m
Di = 0.016 m
f = 0.0004
ϼ = 0.59 Kg/m3
vt = 27.4 m/s
∆Pt = 54.577 N/m2
∆Pr = 4(n)[v2/2g)
∆Pr =306.4 N/m2
∆P = ∆Pt + ∆Pr
∆P = 361 N/m2
Shell Side:
We can calculate pressure drop by using this formula;
f ×G2 × D s ×( N b +1)
∆ P=
2 × g × ρs × Dh × ∅ s
f = 1.9×10−3
Ds = 0.506 m
96
Nb+1 = 15
g = 9.8 m/s
Dh = 1.316 m
Gs = 3.6 Kg/m2.s
ϼs = 814.8 Kg/m3
∆ P=0.0076 N /m2
4.4.5) Specification Sheet for Evaporator:
Unit: Evaporator
Item No: V-1
Type: Forced Circulation
No. of items: 2
Operation: Continues
Heat duty: 2.69915x105 KJ/h
Heat transfer area: 89.25 m2
Overall heat transfer coefficient: 50 KJ/hr-m2 oC
Components Shell side Tube side

Fluid circulated Methanol, water, FAME Steam
Flow rates 438.433 Kg/hr 1730.2 Kg/hr
Temperature Inlet = 55 oC Inlet = 190oC
Outlet = 110 oC Outlet = 115 oC
Material of construction Carbon steel Carbon steel
97
Specifications I.D = 0.5063m OD = 0.019 m, 14 BWG

B = 0.334 m Pitch = 0.0254 m
Length = 4.8 m
Nt = 294
Table 4.6 (Specification Sheet of Evaporator)
Chapter # 5
INSTRUMENTATION AND PROCESS CONTROL
5.1) Objectives:
The primary objective of the designer when specifying instrumentation and control schemes are:
5.1.1) Safe Plant Operation:

98
1. To help the process variables within know safe operating limits.

2. To detect dangerous situations as they develop and to provide alarms and automatic
shutdown systems.
3. To provide inter locks and alarms to prevent dangerous operating procedures.
5.1.2) Production Rate:

In order to achieve the designed production rate.
5.1.3) Product Quality:

To maintain the product composition that desired in market.
5.1.4) Cost:
To operate at the lowest production cost, keep in mind the other objectives. These are not
separate objectives and must be considered together. Measurement is a fundamental parameter
of process control either the control will be affected automatically, semi-automatically or
manually. The quality of the control obtained is a function of the accuracy, repeatable
and reliability of the measuring devices employed. The objective of an automatic process
control is to use the manipulated variable to maintain the controlled variable at its set point in
without disturbances. Instruments are provided to monitor the process variables during plant
operations. Instruments monitoring critical process variables will be fitted with automatic alarms
to alert, the operations to critical and hazardous situations. Pneumatic instruments are used in
this plant. The main process parameters are all indicated in the control room where automatic or
remote control is done. The process parameters e.g. temperatures, pressure flow, liquid level etc.
are converted to signals with transducers and then indicated, recorded and controlled with
secondary instruments.
5.2) Temperature Measurement and Control:

This is used to measure and control the temperature of outlet and inlet streams in heat
exchanger, condenser, heater and column, most temperature measurement in the industrial
processes is made by means of thermocouples. Usually where high measurement accuracy is
required resistance thermometer are used. For the control of temperature, pneumatic feedback
control is used. Outlet temperature of the system is measured with the help of thermocouple.
This temperature is fed to a comparator. The difference between the set point and the input
signal is called error, and then this error is fed to the controller, which controls the valves to
adjust the flow of hot or cooling medium.
5.3) Pressure Measurement and Control:

The temperature and pressure are of much importance for material state and composition. In
fact, these two measurements considered together are the evaluating devices of industrial
99
materials. Most pressure measurement in the industry is made through elastic devices, either
directly connected for local use or transmission type to a location where control is to be done.
5.4) Flow Measurement and Control:

Most flow measurements in the industry are done by variable head devices. To lesser extent
variable area and displacement types are used.
5.5) Control Loops:

For instrumentation and control of different sections and equipment’s of plants, following
control loops are most often used.
1. Feedback control loop

2. Feed forward control loop
3. Ratio control loop
4. Auctioneering control loop
5. Split range control loop
6. Cascade control loop
Here is given a short outline of these control schemes, so that to justify out selection of a
control loop for specified equipment.
5.5.1) Feed Back Control Loop:

A method of control in which a measured value of a process variable is compared with the
desired value of the process variable and any necessary action is taken. Feedback control is
considered as the basic control loops system. Its disadvantage lies in its operational procedure.
For example if a certain quantity is entering in a process, then a monitor will be there at the
process to note its value. Any changes from the set point will be sent to the final control
element through the controller so that to adjust the incoming quantity according to desired
value (set point). But in fact changes have already occurred and only corrective action can be
taken while using feedback control system.
5.5.2) Feed Forward Control Loop:

A method of control in which the value of disturbance is measured before its disturbance then
action is taken to prevent the disturbance by changing the value of a process variable. This is a
control designed to prevent errors from occurring in a process variable. This control system is
better than feedback control because it adds the change in the process variable before it
enters the process and takes the preventive action. While in feedback control system action is
taken after the change has been occurred.
100
5.5.3) Ratio Control:

A control loop in which, the controlling element maintains defined ratio of one variable
to another. Usually this control loop is attached to such a system where two different systems
enter a vessel for reaction that may be of any kind. To maintain the stoichiometric quantities of
different streams, this loop is used so that to ensure the proper process going on in the process
vessel on the basis of stoichiometric calculations.
5.5.4) Auctioneering Control Loop:

This kind of control loop is used for a huge vessel where readings of a single variable may be
different at different points. This type of control loop ensures safe operation because it can
apply all the readings of different points simultaneously, and compares them with the set
point, then the controller sends appropriate signal to final control element.
5.5.5) Split Range Loop:

In this loop controller is preset with different values corresponding to different actions to be
taken at different conditions. The advantage of this loop is to maintain the proper conditions
and to remove faults at different levels.
5.5.6) Cascade Control Loop:

This is a control loop in which two or more control loops are arranged so that the
output of one controlling element adjusts the set point of another controlling element. This
control loop is used where proper and quick control is difficult or faulty with the help of simple
feed forward or feed backward control. Normally first loop is a feedback control loop.
5.6) Control on Distillation Column:

Control on distillation column according to different aspects.
5.6.1) Flow rate and composition control:

101
Fig 5.1 (Composition control loop around distillation column)
Fig 5.2 (Flow Rate control loop around distillation column)
5.6.2) Temperature control loop:

102
The temperature control of the distillation column involves first taking a temperature
measurement and sending it to a distributed control system (DCS). The DCS contains software
which manipulate a control valve that regulates steam flow to the Re-boiler. The block diagram
is below:
Fig 5.3 (Temperature control loop around distillation process)
5.7) Control loop on Reactor:
Fig 5.4 (Temperature control loop around reactor)

103
5.8) Control loop on Heat Exchanger:
Fig 5.5 (Temperature control loop around heat exchanger)
5.9) Control loop on Evaporator:
Fig 5.5 (Temperature control loop around Evaporator)

Chapter # 6
104
PLANT DESIGN ECONOMICS
6.1) Plant cost estimation:
Evaluation of costs in the preliminary design is said predesign cost estimation. As the final
process design stage is completed, it becomes possible to make accurate cost estimation
because detailed equipment specification and definite plant facility information are available.
Direct price quotation based on detailed specification can then be obtained from various
manufactures.
However design project should proceed to the final stages before costs are considered and cost
estimate should proceed be made through out all the early stages of the design when complete
specification are not available.
Such estimation should be capable of providing a basic for company management to decide if
further capital should be invested in the project.
Evaluation of the cost in preliminary design phase is sometime called guess estimations. A
plant design obviously must present a process that is capable of operating under condition
which will yield a profit.
A capital investment is required to any industry process, and determination of the necessary
investment is an important part of a plant design project .The total investment for ny process
consist of the physical, equipment and facilities in the raw materials and products on hand
and handle other special items requiring a direct cast out lay.
6.1.1) Capital investment
Before an industrial plant can be put into operation, large amount must be supplied to purchase
and install the necessary machinery and equipment, land service facilities must be supplied
to obtained and the plant must be erected complete with all pipe controls in service.in addition
it is necessary to have many available for payment of expenses involved in the plant operation.
The capital needed to supply the necessary manufacturing and plant facilities is called the
fixed capital investment while the necessary for the operation of the plant is termed as the
working capital investment.
105
6.1.2) Working capital investment
The capital investment is necessary for the operation of the plant is called working capital
investment.
6.1.3) Fixed capital investment
The capital needed to supply for necessary manufacturing and plant facilities is called
fixed capital investment.
1. Direct cost
2. Indirect cost
Direct cost
The direct cost items are experienced in the construction of the plant in addition to the cost of
equipment.
1. Purchased equipment
2. Purchased equipment installation
3. Instrumentation and control
4. Piping
5. Electrical equipment and materials
6. Buildings including services
7. Yard improvement
8. Service facilities
9. Land
Indirect cost
1. Design and engineering

2. Contractors expenses
3. Contractors fee
Some of the fixed capital investment and working capital investment is known as total capital
investment.
6.2) Purchase Cost of Major Equipment:
The cost of purchased equipment is used as basis of factorial method of cost estimation
and must be determined as accurately as possible Purchase cost of equipment is calculated
106
from graphs and charts available.
Purchase cost = Bare cost from fig. × Factors …… (6.1)
There are different factors used which are Material factor, Pressure factor etc. Cost of
different equipment is calculated as under.
6.2.1) Pumps:
Purchase cost = 8000 $
6.2.2) Reactor:
Area of Reactor = 9.08 m2
= 10,000 × 0.85 × 1.1
= 11,000 $
6.2.3) Evaporator:
C = 4000n = 0.45
Ce = C × Sn
Ce = 4000 × 600.25
Ce = 60,000 $
Total evaporator cost = 2 × Ce = 1, 20,000 $
6.2.4) Distillation Column:

Cost of base vessel = (Cost from Fig.) (Material factor) (Pressure factor) ……. (6.2)
Cost of base vessel = 10,000 × 1.0 × 1.0
Cost of base vessel = 10,000 $
Cost of plates
Cost = (Cost from Fig.) * (Material factor) …… (6.3)
Cost = 700 × 1.0
Cost Per Plate = 700 $/Plate
Cost of total plates = 700 × 10 = 7000 $
Cost of distillation column = 17,000 $
Re-boiler
Cost = 45000 × 1.0 × 1.3
Cost = 58500 $
107
Condenser
Cost = 14000 × 1.0 × 0.85
Cost = 1, 20,000 $
Total Purchased cost of Equipment = PCE = 798077.5 $
6.3) Fixed Capital Cost:

Cost that does not vary with production rate is known as fixed capital cost. These are the bills
to be paid whatever the quantity produced is.
6.3.1) Major equipment, total purchased cost:
 Equipment erection 0.4

 Piping 0.70
 Instrumentation 0.20
 Electrical 0.10
 Building process 0.15
 Utilities 0.50
 Storages 0.15
 Site development 0.05
 Ancillary building 0.15
 Total = 3.40
6.3.2) Physical plant cost:

Physical Plant Cost: = PPC = PCE × (Total Factors)
PPC = 798077.5 × 3.40
PPC = 2,713,463.5 $
 Design and engineering 0.30
 Contractor’s fee 0.05
 Contingency 0.10
 Total 1.45
Fixed Capital = PPC × 1.45

= 2713463.5 × 1.45
= 3934522 $
Thus,
Fixed Capital Cost = FCC = 3,934,522 $
108
Cost in year 2008 = Cost in year 1998 × (Cost index in year 2008/Cost index in 1998)
Cost index in year 2008=1208
Cost index in year 1998=132
Fixed Capital Cost in year 2008 = TFCC = 36,006,838 $
6.4) Operating Cost:
Maintenance cost = 0.10 × Fixed Capital Cost

= 0.10 × 36006838
= 3,600,683.8 $
Miscellaneous = 0.10 × Maintenance Cost

= 0.10 × 3600683.8
= 360,068.4 $
Operating labor = 5 × 105 $

Laboratory cost = 0.20 × labor cost = 1 × 105 $
Supervision = 0.20 × labor cost = 1×105 $
Plant overheads = 0.50 × labor cost = 2.5 × 105 $
Capital charges = 0.15 × fixed capital cost = 0.15 × 36006838 = 5,401,026 $

Local taxes = 0.02 × fixed capital cost = 0.02 × 36006838 = 720,137 $
Insurance = 0.01 × fixed capital cost = 0.01 × 36006838 = 360,068 $
Regulations and license fees = 2 % of Sales Price
6.5) Production Cost:
Variable cost:
Miscellaneous = 360,068.4 $
Shipping and packing negligible (Sub-total) = A = 52,358,828.4 $
Fixed costs
Maintenance cost = 3,600,684
$ Operating labor = 5×105 $
Laboratory cost =1×105 $
Supervision = 1×105 $
Plant overheads = 2.5×105 $
Capital charges = 5,401,026 $
Local taxes = 720,137 $
109
Insurance = 360,068 $
Sub Total B =10,311,778 $
Direct Production Cost = A+B = 62670606.4 $

Sales expense, General overheads, R&D = C = 0.25 × Direct Production Cost = 15,667,651.6 $
Annual Production Cost = A + B + C= 68,338,258 $

Production Cost/Liter = 1.2 $/Liter
110
Chapter # 7
HEALTH & SAFETY
Safety is an important consideration when using any hazardous chemicals – that includes
biodiesel production. There are a multitude of processor configurations, each with its own
specifications and considerations. Many safety considerations are a function of installation,
operation, and supervision. Some modification of commercially purchased systems is often
necessary to maximize safety in individual situations and to meet regulatory guidelines. Here
is the discussion of the most common safety considerations.
7.1) Plant Safety:
7.1.1) Tank Design Safety:

The reaction tank is the main vessel in large-scale biodiesel processor systems. Some tank
design criteria include:
 Temperature/pressure requirements
 Chemical compatibility
 Physical durability
 Ability to be completely sealed (i.e. to be a truly ―closed‖ system)
 Insulation,
 Electrical grounding
 Tank entry (for inspection and cleaning)
In general, the plastic conical has been the tank of choice for small-scale biodiesel processors
because it is less expensive, easy to access for maintenance, allows visibility of the reaction
process, and makes glycerol separation easy. Both pressure and temperature increases are
popular because they can increase the rate of reaction in the biodiesel process. However, plastic
cone-bottom tanks are designed for use at atmospheric pressure and relatively low
temperatures. If pressure or vacuum is applied to the plastic conical tank system, it can cause
excessive deformation or damage to the tanks. Temperatures exceeding the manufacturer are
recommended maximum may also reduce the strength of the tank. Many plastic conical tanks
eventually leak after long-term use. Further, it is difficult to provide adequate electrical
grounding for nonmetallic materials to avoid a static charge that could produce a flash fire or
explosion.
7.1.2) Piping, Tubing, Hoses, Valves, and Gaskets Safety:

Piping, tubing, hoses, valves, and gaskets should meet the system temperature/pressure,
chemical compatibility, and long-term durability requirements. Biodiesel can soften or degrade
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natural rubber hoses and gaskets, leading to fuel leaks and spills. Also, brass, bronze, copper,
lead, tin, and zinc can interfere with the chemical reaction and be corroded by the reaction
chemicals.
7.1.3) Electrical Equipment Safety:

Electrical equipment includes motors, pumps, heating elements, fans, and lighting. Potentially,
these parts can ignite alcohol vapors through arcs and sparks, high surface temperatures, and
electrical equipment failure. The National Electric Code (NEC) has specifications for the design
and installation of electrical equipment in hazardous locations. The selection, placement, design,
and power source of the electrical components should comply with these codes.
The electrically powered pumps (centrifugal or positive displacement) used to transfer and
circulate liquid need specific attention. In general, these pumps are sized between 300gph to
500gph. A hazardous situation can be caused by
 Over-temperature due to deadheading the pump (centrifugal) or a locked rotor.

 Over-pressurized piping if deadheading a positive displacement pump with no internal
pressure relief valve.
 Motor overheating or arcing due to inadequate motor size or improper installation. We
use an explosion-proof motor to prevent an explosion from leaving the motor enclosure.
7.2) Chemicals Safety:
Biodiesel producers should be familiar with the Material Safety Data Sheet (MSDS) for each
chemical used in the biodiesel production process. An MSDS contains comprehensive
information on product identification; ingredients and hazardous classification; physical and
chemical characteristics; fire- and explosion-hazard data; fire-fighting measures; accidental
release measures; health-hazard data; first-aid measures; toxicology; reactivity (and stability)
data; precautions for safe handling, storage, and use; control measures; transportation;
disposal; and regulatory information. MSDSs are available from the chemical vendors.
When handling chemicals, it is important to always wear proper personal protection

equipment (PPE) such as protective gloves, an apron, and eye protection and to not inhale any
vapors. Further, always have running water available. The workspace should be thoroughly
ventilated. Operation should be conducted under a fume hood. No children or pets should be
allowed in the work area. A co-worker should be present to seek assistance. For university
biodiesel production, emergency eye-wash stations and emergency full-body showers are
needed.
Producers should exercise caution when handling methanol and methanol-catalyst mixes
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(methoxide). Methoxide is very caustic and can result in chemical burns. Methanol is a
poisonous chemical that can cause blindness. It can be absorbed directly through the skin or
inhaled as a vapor. Methanol is a flammable liquid with a flash point of 51°F and boiling
point at or above 100°F (depending upon pressure). Therefore, all methanol containers should
be kept tightly closed to prevent evaporation and exposure of people and the environment to
hazardous fumes. When transferring methanol to the catalyst- mixing vessel, always use a
closed circuit. This can be achieved using an explosion-proof induction pump. It is optimal
for the process and also for safety if methoxide is pumped slowly into the reaction vessel via a
closed circuit with an explosion-proof induction pump. Though the mixture gets quite hot at
first, no fumes will escape if the container is kept closed.
Ethanol can be used instead of methanol, although it is less common. Ethanol is bio-based and
has lesser toxicity issues, but is still a chemical and a fire safety concern.
7.3) Containment and Location:
Secondary containment will provide material containment in case of a leak or spills out of the
reaction vessels, storage containers, or piping and tubing of the processor system. We
found no commercial systems that came with secondary containment.
Vessel entry should also be considered. Plastic tanks have screw-top lids that provide the
operator with easy access for cleaning and maintenance. The operator must be cautious when
accessing the tank by opening the screw-top lid. Just because the vessel may be empty does not
mean there are no hazards. Vessels will contain residual chemicals and fumes. The operator
must make sure adequate ventilation and personal protection equipment are used when the
vessel top is removed for inspection, cleaning, or maintenance.
The following is a partial list of common safety considerations for locating a processor:
 Area well ventilated

 No open flames (water heater, clothes dryer or other device nearby)
 Adequate lighting
 Clearances for operation
 Limited access
 Eye-wash station
 Fire extinguisher
 Titration area
 Fume hood (or some other forced draft system that vents to the outside)
7.4) Safety Signs:

113
No placards or warning signs are required for the transport of pure biodiesel. However, biodiesel
blends with diesel and kerosene are required to be transported in placarded trucks if the flash
point of the blend is lower than 200°F (93°C). If the flash point is lower than 140°F (60°C), the
liquid is considered flammable and the Hazard Class 3 flammable placard is required. Between
140° and 200°F (60° to 93°C), the liquid is generally considered to be Hazard Class 3
combustible, and the combustible placard is required for transport. Local fire regulations
determine the requirements for signage on storage containers, but typically, tanks
containing fuels (including B100) must be labeled with NFPA diamonds. The NFPA
diamonds will indicate whether the fuel is flammable or combustible.
Fig. 7.1 (Placards for Transport of Combustible and Flammable Liquids)

114
Chapter # 8
ENVIRONMENTAL ASPECTS
8.1) Environmental impacts of Biofuel:
Same as like petroleum fuels, bio fuels can have environmental impacts at all stages of their
production and use. Relative to fossil fuels, however, the impacts resulting from refining,
transporting and using bio fuels are generally significantly smaller. Moreover, there are ways to
improve the resource efficiency and impacts of these activities.
8.1.1) Water Use:
Large quantities of water can be utilized for processing the lipid feedstock into Biodiesel.
The primary uses of water for biodiesel refining are to wash plants and seeds for processing
and then to remove the soap and catalysts from the oils before and final product is shipped
out. A typical Soybean crushing system requires just over 19 Kg water per ton of oil
produced. For each ton of soybeans that go into the refining process, 170 kg come out as
crude de – gummed soybeans oil, 760 kg are soy meal and remaining 70 kg include air
and solid and liquid waste. The primary contaminant in wastewater is soybean oil.
Production of ethanol, in particular, requires a tremendous amount of water for processing
and for evaporative cooling to keep fermentation temperatures at the required level. But some
feed stocks are more water intensive than other; each ton of sugar cane in Brazil, for
example, requires as much as 3900 liters for processing.
Ethanol processing also results in large volumes of nutrient rich wastewater that, if not
cleaned and recycled can speed eutrophication of local rivers and streams by affecting the
water’s dissolved oxygen content. In addition, sugar mills must be flushed every year,
putting huge amount of organic matter into local waterways. In Brazil, 1 liter of ethanol
produces about 10 to 15 liters of vinasse which is very hot and corrosive, with a low pH and
high mineral content. Today, however, wastewater and vinasse are recycled and used for
irrigation and fertilization of Brazil’s sugarcane crops, with varying quantities of vinasse used
under different conditions as regulated by law. However, some experts caution that vinasse
cannot be used where water tables are high, such as in India.
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8.1.2) Air pollution:
Among the pollutant that bio refineries emit in to the air are SOx, NOX, VOCs and particulate
matter. Emission from corn ethanol plants, for example include SOx, NOx, CO, mercury,
particulates and CO. Corn ethanol plants in low a have polluted both water and air, emitting
cancer causing chemicals such as formaldehyde and toluene.
Biodiesel production require methanol, which has the same environmental cost as those
associated with petroleum production. In addition, direct emission from biodiesel
processing plants can include air, stream and hexane, which can be used to extract oil from
plants and seeds. Hexane is air pollution, and through as much as possible is recovered and
recycled, some is emitted into air as well. It is estimated that soybean crushing system releases
just over 10 Kg of hexane per ton of oil produced. Alternatives have been found so that
hexane is no longer needed; but these options are more costly. In addition, where renewable
sources are not used to produce process energy, pollutants associated with the use for natural
gas and the generation of steam and electricity are released into air. An estimated 3.6 Kilowatt
hour of electricity is required per ton of soybeans entering in a soy biodiesel plant.
As plant size increases, concerns about pollution – including air emissions, odor releases during
the drying of distiller’s grain in corn ethanol plants and waste water recharges- have risen as
well. However, with appropriate regulation and pollution control technologies, emission
associated with bio fuels refining can be minimized significantly. For example NOx emission
from boiler can be reduced by installing new NOx burner system. VOCs emission, which
results primarily from the blending of ethanol with gasoline, can be reduced by mixing fuels at
locations where pollutants can be collected and treated. In some cases, new and larger plants
are incorporating such emission control system and are finding alternative options that are
enable them to reduce such emissions.
In addition, much of the air pollution associated with bio fuels refining results from burning
of fossils fuels for process heat and power – which in the US, Germany, China and many other
countries is mainly coal. Thus, emission can be reduced through traditional power plant control
technology or the use of renewably generated power.
In Brazil, today, mills and distilleries meet most if not all of their own energy needs bagasse ( a
byproduct of sugar cane crushing), which can generate thermal, mechanical and electrical
energy. Some plants even sell surplus electricity into the grid. Elsewhere, agricultural and
forestry residues can be used to produce required power and heat; however it is important to
ensure that enough residues remain to maintain soil organic matter and nutrient levels.
8.2) Environmental Laws for Biodiesel Plants:

116
8.2.1) Clean Water Act:
A biodiesel production facility typically uses water for cooling and for washing the biodiesel
product to remove impurities. Some small biodiesel operators may use resin instead of water to
remove impurities, discussed in Pollution Prevention Appendix G of this manual. Those
facilities using water will generate wastewater, which can include cooling tower blow down,
boiler blow down, and water softener discharge. These wastewater streams are not concentrated
wastes. The wash water contains glycerin, methanol, unreacted feed oils, and some biodiesel.
The wash water is a high strength waste.
In addition, storm water runoff from the facility may be contaminated from precipitation (rain
or snow) coming in contact with facility operations and requires adequate control and
management.
Wastewater Discharge Permits:
Wastewater from a biodiesel facility can be disposed in various ways. The method of disposal
determines what kind of permit is needed and what permitting authority will issue it. In general,
there are three alternatives for the disposal of wastewater:
 Direct discharge to a receiving stream

 Discharge to a municipal wastewater treatment system
 Land application
Permits for Disposal Directly to a Water Body:
Any discharge directly into a water body—for example, a stream, river, or lake; or by
conveyance by a pipe or culvert to a water body, must be permitted prior to discharge. These
permits are issued by the state in which the biodiesel facility will be located under the National
Pollutant Discharge Elimination System (NPDES), the federal water pollution control program
created by the Clean Water Act.
An NPDES permit regulates the amount of pollutants that can be discharged. The permit writer
will establish limits in the permit that protect the water quality of the receiving water body. In
addition to numeric effluent limitations, NPDES permits will include monitoring, reporting, and
record keeping requirements. Permits are required whether or not on-site treatment occurs.
To receive an NPDES permit, a written application must be made with the respective state
agency 180 days prior to commencing discharge. The application will consist of multiple forms
covering different aspects of the discharge. In general, the application forms will include:
117
 General Information
 Existing Industrial Wastewater
 New Source and New Discharger Industrial Wastewater
 Non-Process Wastewater only
 Storm water Discharges Associated with Industrial Activity
For further information, refer to the state contact information in Appendix A under CWA
National Pollutant Discharge Elimination System (NPDES) Permits.
Permits to Discharge to a Municipal Wastewater Treatment System:
Most of the larger cities implement an Estate-approved pretreatment program to prevent

wastewater discharges from having a deleterious effect on their treatment plant, collection
system, and the water body into which they discharge. Cities with pretreatment programs issue
permits to significant industrial users, which are those facilities that discharge a minimum of
25,000 gallons per day of wastewater, 5% of the receiving wastewater treatment plant’s
capacity, or have been determined by the city to have significant potential to affect their plant
and its operations. The city will require a permit application be filed with the city pretreatment
coordinator prior to discharge. The amount of time required for the permit application to be
filed prior to discharge can vary but may be as long as 180 days. The pretreatment permit will
contain numeric limits based on local treatment plant capabilities and environmental
conditions. In addition, the permit will also contain monitoring, reporting, and record keeping
requirements.
Permits for Land Application for Wastewater Disposal:
There are no federal regulations that apply to wastewater that is properly disposed by land
application. However, land application of wastewater may be covered by an NPDES permit
(storm water or non-storm water) where it is determined that pollutants run off the application
site to a water administer programs that establish proper land application procedures to ensure
that wastewater is applied at agronomic rates, which are rates that plants assimilate the nutrients
in the wastewater without pollutant loss through runoff.
8.3) Safe Drinking Water Act:
8.3.1) Public Water System Supervision Program:
If your facility uses its own water supply source to provide drinking water to 25 or more
118
people per day for at least 60 days of the year, then you are required by the Public Water
System Supervision Program to obtain permits for the construction/modification and operation
of the water supply system. Even if you only use your own water source for supplying cooling
or industrial processing water, there are several state-issued water-supply related permits that
might be required. These include:
Water Use Permit: Withdrawing or using water from a surface or underground source
typically requires a water use permit, depending on the volume of water that will be used daily.
Any increase in water withdrawal/use could require a modification to an existing water
use permit.
Well Construction Permit: Drilling a new well or modifying an existing well requires a well
construction permit.
Operator Certification: Every public water system must be operated by a trained and
qualified operator who is responsible for the quality of the water and meeting the regulatory
requirements. States have programs for training and certifying operators at a level appropriate
to the level of water treatment at the facility. It is the responsibility of the water system
owner to have a certified operator in charge.
Routine testing: Your drinking water must be tested for compliance with all the federal and
state drinking water standards. The cost of sampling and analysis is the responsibility of the
water system owner. Standards are set for microbiological contaminants, man-made
chemicals and pesticides, naturally-occurring inorganics, and contamination caused by human
activity, such as lead and nitrates. There are also requirements for operational testing, record-
keeping and reporting, correction of sanitary deficiencies, and notification of the public when
problems occur.
It is important that facilities planning to develop their own water supply or modify their
existing source(s) first check with the state environmental, health or natural resources
office listed in the public water system supervision section of Appendix A to ensure that all
of the necessary permits are in place before proceeding.
If your facility is using water from an existing water supply system such as a municipal water
supply for your drinking water source, then the Public Water System Supervision Program does
not apply. However, if you also plan to use this existing water supply as the source of cooling
or industrial processing water, you should check with the system operator to make sure the
system can provide a sufficient quantity of water for your needs. This is important for
industries which need large quantities of water for manufacturing or processing.
119
8.3.2) Underground Injection Control Program:
The Underground Injection Control program regulates wells that are used by cities, agriculture,
business and industry to inject fluids underground for disposal, hydrocarbon production and
storage, or mineral recovery. The program defines an injection well as any bored, drilled or
driven shaft or dug a hole, where the depth is greater than the largest surface dimension of the
well and is used to discharge fluids underground or a subsurface fluid distribution system. This
definition covers a wide variety of injection practices that range from technically sophisticated
and highly monitored wells that pump fluids into isolated formations up to two miles below the
Earth's surface to the far more numerous on-site drainage systems, such as septic systems,
cesspools, and storm water wells which discharge fluids a few feet underground. The program
requirements are designed to ensure that injected fluids stay within the wells and the intended
injection zones and do not endanger underground drinking water sources. No injection is
authorized without approval from the appropriate regulatory authority.
Injection practices not regulated by the underground injection program include individual
residential waste disposal systems that inject ONLY sanitary waste and commercial waste
disposal systems that serve fewer than 20 persons that inject ONLY sanitary waste.
A biodiesel plant is subject to the requirements of the underground injection

program if:
 It is disposing of storm water, cooling water, industrial or other fluids into the
subsurface via an injection well; or
 It has an on-site sanitary waste disposal system; for example, a septic system that
serves or has the capacity to serve 20 or more people; or
 It has an on-site sanitary waste disposal system that is receiving other than a solely
sanitary waste stream, regardless of its capacity; or
 It is undergoing a remediation process where fluids are being introduced into the
subsurface via an injection well to facilitate or enhance the cleanup.
Facilities that discharge fluids to streams, ponds, lagoons, or treatment facilities are not subject
to the provisions of the underground injection program but could be regulated by the Clean
Water Act.
It is important that facilities planning on using a new injection well or modifying an existing
one check with the state environmental, health or natural resources office listed in the
underground injection section of Appendix A to make sure that all of the necessary permits or
approvals are in place before proceeding.
120
8.4) Clean Air Act:
8.4.1) Air Operating Permits:
A biodiesel plant might need to obtain an air permit for day-to-day facility operations.
There are two types of operating permits:
1. Major Source Title V Air Permits

2. Minor Source Air Permits
The potential emissions from the plant will determine whether a facility will obtain a major or
minor operating permit.
Major Source Air Permits:
The federal operating permit program was created by the Clean Air Act Amendments of 1990
and was designed to create a ―one stop‖ permit. The Title V operating permit compiles all of
the applicable state and federal regulatory requirements, existing construction permit
provisions, record keeping, reporting, testing, and monitoring requirements into one permit.
The intention behind listing everything in one permit is to help facilities maintain
compliance. It is common for a facility to have several construction permits for several pieces
of equipment, and it is difficult to keep track of all of the requirements in each permit. One
permit with all of the facility’s requirements is intended to make it easier to track the
requirements.
Public notification is also an important aspect of the operating permit program. The public
is notified when an operating permit is proposed and is given the opportunity to comment
during the 30-day public notice period. This also gives the public an opportunity to learn about
the effects the facility might have on the environment.
Unlike a construction permit that must be obtained prior to construction and is valid for the
entire life of the emission unit, an operating permit must be applied for within some period
(often 12 months) after the facility begins operation. The operating permit is generally issued
for a specific period of time (usually for five years) rather than the life of the operating unit.
A biodiesel plant would need to obtain a Title V operating permit if the plant has potential-to-
emit quantities greater than 100 tons per year of any criteria pollutant or is a major source of
hazardous air pollutants.
121
Minor Source Air Permits:
A biodiesel plant can limit the facility’s potential to emit to less than the Clean Air Act major
source thresholds by accepting operational limits in a minor source operating permit. However,
minor sources have less operational flexibility because they must keep their emissions below
the major source threshold.
Minor operating permits are not subject to review by EPA.
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Chapter # 1: 1.1) What Is Biodiesel?

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1

1.2) Raw Material (Micro-Algae):

Table 1.1 (Oil Contents of some Micro-algae)

Fig 1.1 (General Process Description of Biodiesel)

1.3) Biodiesel Properties:

1.3.1) Chemical Composition of Biodiesel:

Table 1.2 (Elemental composition of diesel fuel and biodiesel, % (m/m))

1.3.2) Cetane Number:

1.3.3) Heat of Combustion:

1.3.4) Biodiesel Density:

Table 1.4 (Density and viscosity of fatty acid esters)

1.3.5) Biodiesel Viscosity:

1.3.6) Cold flow properties:

1.3.6.1) Cloud point: (CP)

1.3.6.2) Pour point: (PP)

1.3.6.4) Low-temperature flow test: (LTFT)

1.3.6.5) Cold soak filtration test (CSFT)

1.3.7) Biodiesel lubricity:

lubricity quality standards

1.3.8) Flash point: (FP)

1.3.9) Acid value:

 Residual mineral acids from the production process

1.3.10) Iodine value:

1.3.11) Biodiesel stability:

 Long-term storage stability or aging.

 The Rancimat test

1.3.12) Water and sediments:

1.3.13) Other Properties:

1.4) Biodiesel Applications:

1.5) Advantages and Disadvantages of Biodiesel:

1.6) Monitoring the Biodiesel Quality:

1.7) Process Available and Capacity Selection:

1.7.1) Process Available:

 Mechanism of trans-esterification reaction

Enzyme-catalyzed trans-esterification for the production of Biodiesel is not preferable as

 Low reaction rate.

1.7.1.2) Base-catalyzed trans-esterification:

 Soap formation due to the presence of FFA in large quantity

1.7.1.3) Acid-catalyzed trans-esterification:

1.7.2) Process Selection:

1.7.2.1) Process Description:

1.7.2.1.1) Algae Transportation:

1.7.2.1.3) Lipid Extraction (Leaching):

1.7.2.1.4) Solvent Recovery (Distillation):

1.7.2.1.6) Separation of Methanol (Distillation):

1.7.2.1.7) Neutralization and Separation:

1.7.2.1.8) Biodiesel Purification/Washing:

1.7.4) Capacity Selection:

3.04 MT 1 year 106 Tons 1000 Kg 8.328767 ×106 Kg 8328.767 T

10000 Liters 883.4 Kg 1 m3 8834 Kg 8.834 T

2400 Liters 834 Kg m3 20 400.32 Kg

0.3970 m3 100 g biomass 920 Kg Kg

The General mass transfer equation is,

2.1) Expeller Balance: (C-1)

As in general mass balance equation (2.1),

Rate of mass∈¿ Rate of mass out

75% Extraction Remaining lipids= 91.42 Kg/h

2.2) Extractor Balance: (E-1)

As in general mass balance equation (2.1),

= 403.81[2.47(68.73-25) + 335.5 + 1.908*(80-68.73)] = 187699.5 KJ/h