Seminar Report on

Reactive Distillation for Biodiesel Synthesis

Submitted By: Pratham Sehgal

Guide: Prof. Srinivas

IIT BOMBAY
Abstract

Rapid economic expansion and growth in the world’s population have certainly
prompted an increase in energy demand. With the increasing demand for fuels, it is
obligatory to find alternatives to decrease the environmental hazards they create.
Biofuels have turned out to be a convincing and promising renewable and clean fuel
option. In recent years, biodiesel has come up as a promising alternative to standard
crude oil-based diesel fuel. the report highlights the synthesis of biodiesel using
different reactive distillation techniques. The main process of transesterification with
different combinations of feedstocks, catalysts, reactors, and new processing
technologies developed in recent years has been discussed and analyzed at length. In
the end, the reviews of the current and future scope of biodiesel have been discussed.
 Table of Content

Introduction:
 1. Introduction:
The economic expansion and human population have been ever-increasing since
ancient times and so has the energy demand. The current world population of 7.6
billion is expected to increase by 25 percent in the upcoming 25-30 years. By using
the data above the world’s two major energy organizations, the international energy
agency and energy information administration have extrapolated past and current
trends in energy consumption and forecasted the energy we will need in the future.
Many studies forecast that the world will run out of oil 2030 and other fossil fuels by
2050.

The increasing energy demands have not only led to the substantial depletion of
nonrenewable crude oil reserves but also worsened global warming and affected the
temperature and climate of the earth which are exerting a profound impact on the
current human generation. As a result, issues concerning fuel depletion and
environmental deterioration have prompted analysis to look for different renewable
energy. Among the potential candidates, biodiesel has emerged as a promising
alternative to crude oil-based diesel.

Biodiesel has attracted and developed an interest in various energy organizations,

governments, and the general public as well. It has been proven to be the best
substitute for fossil-based fuels due to its environmental advantages and renewable
resource availability. Biodiesel is produced from edible or non-edible oils, animal
fats, and waste cooking oil through a process called transesterification. This process
is supported by the addition of catalysts.
Apart from biodiesel, the process of transesterification also produces glycerol as a
by-product. The glycerol comes in handy to produce an anti-knocking agent. The
standard prevailing method requires the transesterification of oils to be reacted in a
batch reactor and the typical catalyst is a homogeneous liquid base catalyst. The
batch reactor for large-scale production requires high investment and operational
costs. Also, the homogenous catalyst cannot be further regenerated or used after the
reaction. Thus, there is a need to look for alternative methods which could not only
reduce the cost of production but also increase productivity.

1.1 Continuous Reactive Distillation:

Continuous reactive distillation(RD) is one such candidate which is capable of
reducing the production cost as well as improving efficiency thereby making the
price of biodiesel combative to crude oil-based diesel.
Reactive distillation is an integrated system of reaction and separation processes
designed in a single column. It has certain advantages over conventional distillation
techniques. These are as follows :
1. Higher conversion
2. Lower energy consumption
3. Longer Catalyst life
4. Reduction in capital and operational cost and
5. Voidance of azeotropes

Many methods have been proposed and simulation approaches have been
typically used to model biodiesel production using different catalysts (i.e.,
alkali, acid or heterogeneous alkali), feedstock (pure vegetable oil or waste
cooking oil), and reaction conditions (normal or supercritical). These studies
aimed to optimize the column’s performance and maximize product
(biodiesel) yield.
Figure 1. Illustration of biodiesel Synthesis in Reactive Distillation.

2. Methodologies:
 Several different techniques have been applied for biodiesel production with
different combinations of transesterification, different catalysts, different feedstocks,
and reaction conditions.To mimic the operation of reactive distillation for the
production of biodiesel, numerous software programmes and simulation processes
have been used. Following are a few of these:

2.1 Homogeneous Alkali Catalysts Processes :

Homogenous alkali-catalyzed process using edible oils was carried out to
produce biodiesel. Due to low free fatty acids content(less than 0.3%), pure soybean
oil was used as process feedstock as it prevents the pre-treatment process.The
biodiesel produced through this process is commonly known as first-generation
biodiesel.The transesterification reaction pathway for alkali catalysed process is
described by the following three equations:

TG + MeOH ➜DG + ME (1)

DG + MeOH➜ MG + ME (2)
MG + MeOH➜ GL + ME (3)

[TG] , [DG] , [GL] , [ME] , [MG] and [GL] are the molar concentrations of
Triglyceride, Diglyceride, Monoglyceride, Methanol, Methyl Ester and Glycerol
respectively.The alcohol reacting with the soybean oil is excessive, and the alcohol-
to-oil mole ratio in the inlet is kept at 6:1. Additionally, the homogeneous catalyst
has been generically classified into the following two categories:

Figure:
2.1.1 Homogeneous Liquid Catalysts:

1) Hydrochloric acid:
Transesterification of beef tallow with methanol in the presence of hydrochloric acid
has been used in one of the studies. The study investigated the relationship between
reaction time, catalyst concentration at constant methanol, and reaction temperature.

2) Sulphuric acid:
Sulphuric acid has been identified as a promising candidate for esterification of
vegetable oils with high FFA levels. For the synthesis of biodiesel, various
feedstocks such as soybean oil, crude palm oil, Jatropha curcas, and waste cooking
oil (WCO) have been combined with sulphuric acid as a catalyst.

3) Phosphorous acid:
A scheme has been propounded to produce biodiesel from low-cost feedstock such
as cotton seed oil by using super phosphoric acid as a catalyst.On the conversion of
biodiesel, the impacts of several physicochemical parameters, such as temperature,
the molar ratio of palm fatty acid distillate to methanol, and the quantity of catalyst,
have been studied.

2.1.2 Homogeneous Solid Catalysts

1) Potassium hydroxide:
A study used homogenous alkali, specifically KOH, as a catalyst to produce
biodiesel using Jatropha oil as a feedstock. The feedstock was converted to biodiesel
via transesterification in the presence of a methanol/KOH combination. In addition
to regular stirring of the mixture for 1.5 hours, the reaction temperature was kept at
50°C, 60°C, and 70°C.

2) Sodium Hydroxide:
Using sodium hydroxide as a catalyst, transesterification reactions of four distinct
vegetable oils—sunflower, rapeseed, olive, and used frying oil—with ethanol have
been studied. For the conversion of sunflower oil, the effects of the catalyst mass
ratio to oil (0.25 to 1.5%), the ethanol molar ratio to oil (6:1 to 12:1), and the
reaction temperature (35 to 90 °C) have been noted.

2.2 Heterogeneous Alkali Catalysed Process

The use of a heterogeneous solid catalyst is proposed as a potential solution to the
conventional method of production of biodiesel.The heterogeneous catalysts have
been classified into the following categories:

2.2.1 Solid Base Catalysts :

1) SrO metal oxide for transesterification of soybean oil :

SrCO3 was calcined for approximately 5 hours at a temperature of 1200 degrees
Celsius in order to prepare the catalyst. The creation of an ionic compound by SrO
and methanol is the key procedure. The conversion achieved was 95% at 65 C, 3
weight percent catalyst concentration, 12:1 molar methanol to oil ratio, and 30
minute reaction time.

2) CaO as solid catalyst for transesterification of soybean oil:

The reaction was carried out with a 12:1 molar ratio of methanol to oil. When the
process was run for 3 hours, the biodiesel production was 95%. It was also
discovered that CaO maintained activity for a longer period of time (20 cycles), even
after being used repeatedly, and that bidodiesel yield was unaffected, as opposed to
alkali metal compounds such as K2CO3/γAl2O3, which dissolve in methanol,
lowering biodiesel yield after each cycle of use.

3) MgO-catalyzed transesterification reaction:

A three-step "Eley-Rideal" type kinetic model was proposed, with the assumption
that methanol adsorption served as the rate-determining phase. A continuous
generation of 100,000 tonnes of biodiesel per year can be accomplished in a 25 m3
stirred reactor with 5700 kg of MgO catalyst.

4) NaX Zeolite loaded with KOH

NaX zeolite loaded with 10% KOH (KOH/NaX) was reported as a base catalyst in
soybean oil transesterification performed.NaX zeolite was dried at 110 C for 2 hours
before being impregnated with an aqueous solution of KOH for 24 hours, followed
by drying and heating at 120 C for 3 hours. The reaction was carried out at a reflux
temperature of 65 C, with a methanol-to-oil ratio of 10:1 M and 3 wt.% catalysts.
Within 8 hours, 85.6% conversion was achieved.

2.2.2 Acid Solid Catalysts:

1) Vanadyl Phosphate
It has been proposed to use vanadyl phosphate (VOP) as a catalyst in the
transesterification of soybean oil. They discovered that the catalyst was active in the
transesterification reaction, with 80% methyl ester yield produced after just 1 hour of
reaction time, despite the fact that the specific surface area of the catalyst was
modest (2-4 m2 /g).

2) Sulfated Zirconia For Transesterification

Sulfated zirconia solid acid catalyst was studied for the transesterification reaction of
soybean oil and simultaneous esterification of oleic acid with methanol and ethanol
in a high-pressure reactor by Garcia et al. (2008). Sulfated zirconia was prepared by
either solvent free method (S-ZrO2) or the standard precipitation method (SZ). In the
solvent-free method ZrOCl28H2O and (NH4)2SO4 are mixed in a molar ratio of 1:6
for 20 min at room temperature and calcined at 600 C for 5 h

3) Zirconia-supported Tungsten Oxide

The solid acid catalyst zirconia supported tungsten oxide (WO3/ZrO2) has been
investigated for esterification of palmitic acid with methanol. The catalyst was made
by impregnating zirconium hydroxide gel with ammonium meta tungstate containing
2.5-25 wt.% WO3. The catalyst was dried before being calcined at 500 degrees
Celsius. In 6 hours of reaction time, a maximum conversion of 98% was recorded
using 5% WO3/ZrO2 catalyst.

2.2.3 Acid Base Solid Catalysts:

Cheaper feedstocks, such as waste oils and animal fats, cannot be converted to
biodiesel using the traditional base-mediated process because the FFA in oils causes
saponification issues. Although acids can esterify FFA, the sluggish rates and the use
of expensive metals make it less popular. Heterogeneous catalysts with both acidic
and basic sites have been explored for their ability to esterify FFA while also
transesterifying triglycerides to biodiesel.

1) Mesoporous calcium, magnesium silicate, and barium silicate

By forming a mixed oxide from strong basic metal oxide (mesoporous Calcium) and
weak acidic silica(barium silicate, magnesium silicate), the acidity of silica was
significantly enhanced. To transesterify soybean oil at a conversion level of 90%–
100%, the catalyst proved effective. It was reported that the conversion process took
more than 26 hours and the effective temperature range was 80 degC.

2) Mixed metal oxide mesoporous silica material

Mixed metal oxide mesoporous silica material has been used for TG
transesterification and simultaneous esterification of FFA.These mixed metal
catalysts made of mesoporous calcium silicate with varying amounts of calcium
oxide were formed. These catalysts were able to esterify the free acids as well as
soybean oil in methanol in 24 hours at 80 C.

2.3 Supercritical Condition:

Biodiesel can also be manufactured by employing supercritical alcohols, which
eliminates the need for a catalyst and reduces the number of separation units. The
triglycerides from vegetable oils or animal fats are transesterified with methanol
under supercritical conditions, i.e. 350 C and 20-50 MPa. A two-step process has
been developed to minimise the intensity of the reaction conditions. Triglycerides
are first processed with water to extract fatty acids and glycerol, which are then
removed. At 270 C and 7 MPa, the fatty acids react with methanol to produce methyl
esters (biodiesel) and water.
 Fig: Two step process for Super critical process

3. Results and Discussion

biodiesel production using the reactive distillation technique has been proven to be
economical as well as feasible compared to the conventional process for the
production of biodiesel.
Various simulations and analysis methods have been implemented in several studies
to get the best parameters for the production of Biodiesel.
Below is the table which summarizes the homogeneous alkali catalysts and the
corresponding parameters:
 Catalyst Reaction parameters
type
Feedstock Molar ratio Temperature Yield Time

HCl Frying oil 8:1 60deg 99.0% 8h

H2SO4 Waste tallow 30:1 50 deg 99.01 ± 0.71% 24h

H3PO4 Cotton seed oil 12:1 70deg

KOH sunflower 6:1 70deg 99.5%

cooking oil

NaOH palm kernel oil 6:1 60deg 95.8% 1.5h

Table: Homogeneous Catalysts and Corresponding Reaction Parameters

Catalyst type Reaction Parameters

Feedstock Molar ratio Temperature Yield

Time

SrO Soybean oil 12:1 65deg 95% 0.5h

CaO Sunflower oil 6:1 60deg 98% 2h

MgO+K2CO3 Soybean oil 10:1 70deg 99.5% 3h

NaX/Zeolite Soybean oil 10:1 65deg 95.1% 8h

Table: heterogeneous catalysts for Biodiesel Production

The type of catalyst employed greatly affects how well vegetable oil converts to
biodiesel. As a result, one of the primary determinants of the rate and yield of
biodiesel throughout the biodiesel manufacturing process is the catalyst.
One of the most crucial problems being debated by industries is the choice of
catalyst to employ in the creation of economically feasible biodiesel fuel. NaOH and
KOH are commonly used because they are less expensive than alkoxides but are less
active. The paper[] shows that separation of esters is easier when KOH as a catalyst
is used compared to NaOH, and CH3ONa.The researchers found that acid-catalyzed
transesterification using used cooking oil was more economically feasible.

Furthermore, heterogeneous catalysts have numerous advantages over homogeneous

catalysts, such as catalyst re-usability, reduced separation and purification issues,
high purity glycerol (above 99%), and catalyst recoverability. Furthermore, there is
no need for a neutralising step.

Future Challenges:
To make biodiesel production process cost effective, the chemistry of heterogeneous
catalysts such as solid alkaline catalysts needs to be thoroughly explored, developed
and use consistently in producing biodiesel. Further the catalysts were found provide
biodiesel yield similar those obtained from homogeneous alkaline catalysts.

The development of enzymes catalyst as a more environmentally benign process is

necessary due to the prevailing environmental needs. Besides the process is potentially
sound providing high-quality biodiesel fuel that can compete favorably with petro-
diesel fuel
Conclusions
Use of high FFAs feedstocks to produce biodiesel is more economically viable,
though it has great negative effects on the catalyst. Besides refining of crude
biodiesel produced from low quality feedstock with alkaline catalysts is complicated.

It was found that acid-catalyzed transesterification reaction needs higher alcohol to oil
molar ratios. In addition the reaction was reported to cause large corrosion effects on
the production facilities.

It observed that biodiesel can be conveniently produced from low quality feedstocks
using heterogeneous catalysts. Especially, enzymatic-catalyzed transesterification
reaction that was discovered to converts FFAs to biodiesel fuel.

The conversion of FFAs to biodiesel was found to increase the yield of biodiesel and
simplify the separation of catalyst form crude biodiesel mixture.