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Abstract

Renewable energy research is receiving increased attention in recent years. Main reasons for this evolution are energy,
economic and environmental security related concern ,one of the energy is biodiesel .

Biodiesel is a good alternative fuel to petroleum diesel. It is produced through Transesterification Reaction between vegetable
oil or animal fats and alcohol , biodiesel produce via microwave assisted process and ultrasound assisted process .

The preparation of biodiesel using a scientific microwave apparatus offers a fast, easy route to this valuable biofuel with
advantages of a short reaction time, a low oil/methanol ratio, and an ease of operation. The methodology allows for
the reaction to be run under atmospheric conditions; it is complete in a matter of a few minutes and can be performed
on batch scales up to 3 kg of oil at a time ,

on the other hand ,Ultrasound irradiation causes cavitation of bubbles near the phase boundary between the alcohol and
oil phases. The asymmetric collapse of the cavitation bubbles disrupts the phase boundary. The cavitation may also lead
to a localized increase in temperature at the phase boundary, enhancing the transesterification reaction. Neither additional
agitation nor heating is required to produce biodiesel by ultrasound technique.

Table of Contents

Abstract ....1

Table of Content ...2

1: Introduction .....3

2: Production of biodiesel via microwave assisted process .............6

3: Microwave role in biodiesel production ...................7

4: Microwave based biodiesel production......................9


4.1 Edible oils (first generation)
4.2 Non-edible oils (second generation)
4.3 Algae and other feedstock (third generation)

5: Production of Biodiesel via Ultrasound assisted process ..........11


5.1 How ultrasound work ?
5.2 Ultrasound for Biodiesel Processing

6: Biodiesel conversion Using Ultrasonication...13

7 : conclusions ......................15

8: References ....16

1: Introduction

Renewable energy research is receiving increased attention in recent years. Main reasons for this evolution are energy,
economic and environmental security related concerns. It is reported that the present petroleum consumption is 105 times
faster than the nature can create at this rate of consumption, the worlds fossil fuel reserves will be diminished by 2050.
Apart from this, the fuel consumption is expected rise by 60% or so in the next 25 years.
To reduce dependency on the fossil fuel sources and imports from oil-rich countries and maintain environmental sustainability,
many countries have committed to renewable energy production increases and greenhouse gas emission reductions at
national and international levels.
Among many renewable energy sources solar thermal and photovoltaic collectors are still not mature and are cost-prohibitive.
For instance, energy conversion efficiency of the photovoltaic modules available in the market is at the maximum of 15%.
Photovoltaic cells are also referred to as solar energy harvesting factories with an input to output ratios of 1:7. The return
energy production rate from the photovoltaic modules is slow over 20-25 years [5]. Wind and geothermal sources have
limitations such as location, availability, and intensity. Since most of the transportation and industrial sectors need liquid
fuels to drive the machinery and engines, more emphasis is needed on alternative fuel sources such as biodiesel.
Biodiesel is composed of methyl or ethyl esters produced from vegetable oil or animal oil and has fuel properties similar to
diesel fuel which renders its use as biofuel.

Biodiesel offers many benefits:

serves as alternative to petroleum-derived fuel, which implies a lower dependence on crude oil foreign imports;
provides favorable energy return on energy invested;
reduces greenhouse emissions in line with the KyotoProtocol agreement;
lowers harmful gaseous emissions
biodegradable and nontoxic fuel, being beneficial for reservoirs, lakes, marine life, and other environmentally sensitive areas

It has been realized that local biodiesel production can address challenges related to energy independence, economic
prosperity, and environmental sustainability in any nation. Towards this end, the United States (US) and Europe have
encouraged large scale industrial biodiesel production. For example, biodiesel production in the US has increased from 75
million gallons in 2005 to 250 million gallons in 2006 and 450 million gallons in 2007, with an expected total capacity of
well over 1 billion gallons in the next few years. Also, the federal government has passed the energy independence and
security act (EISA) in 2007 which requires a gradual increase in the production of renewable fuels to reach 36 billion gallons
per year by 2022. Furthermore, 28 states have passed their own mandatory renewable energy legislation. For example,
Arizona and California will replace 15% and 20% of their electricity sales with renewable energy by 2020, respectively.
Texas has a mandate for 5880 MW of renewable electricity capacity by 2015. Other states have mandates to reduce
greenhouse gas (GHG) emissions. For instance, Minnesotas strategic goal is to reduce GHG emissions by 80%
between 2005 and 2050

Local biodiesel production holds great promise to solve the above mentioned energy and environmental related concerns;

however there are two major challenges that inhibit biodiesel production:

cost of the feedstock; and


conversion process of oils to biodiesel. While using low cost feedstock and recycling waste cooking oils and animal fats can
be an alternative to reduce the feedstock costs; process improvements and optimization help reduce the biodiesel conversion
process costs.

Biodiesel production involves two main steps

extraction of oils from the feedstock, and


conversion (transesterification) of oils (fatty acids) to biodiesel (alkyl esters).

Without these steps biodiesel production is not possible, as such, these two steps play important role and need detailed
attention.Common methods employed to demonstrate these two steps simultaneously or in series include conventional
heating, high pressure and temperature reactions such as thermal liquefaction and pyrolysis. These methods are
employed based on the feedstock type and quality. These methods are not energy-efficient and are expensive and offer
scope for further improvements. Several process modification and improvements were performed both at laboratory
research and industrial levels

In this category, the effect of radiofrequency and ultrasound waves has been tested:
Ultrasonic production has shown improvements in extraction and transesterification processes; however, the technology
may require longer reaction times and larger volumes of solvents possibly with excess energy consumption compared
to microwave based process.

Recently, microwaves have received increased attention due to their ability to complete chemical reactions in very
short times . Microwaves have revolutionized the way chemical reactions can be performed with unexplainable results. This
amazed the entire scientific and industrial community and resulted in curious chemists who applied microwaves in different
areas of chemistry to benefit from these results

Few advantages with microwave processing can be listed as:

rapid heating and cooling;


cost savings due to energy,
time and work space savings;
precise and controlled processing;
selective heating;
volumetric and uniform heating;
reduced processing time;
improved quality (reportedly) and properties;
effects not achievable by conventional means of heating

Microwaves have been used by many researchers around the world in many organic and inorganic syntheses at exploratory
levels. Recently, many industries have successfully implemented microwave based processes, examples include:
ceramic/ceramic matrix composite sintering and powder processing, polymers and polymer-matrix composites processing,
microwave plasma processing of materials, and minerals processing.
Microwaves have the ability to induce reactions even in solvent-free conditions offering Green Chemistry solutions to many
environmental problems related to hazardous and toxic contaminants.

Due to these advantages, microwaves provide for tremendous opportunities to improve biodiesel conversion processe
from different feedstock and oils. The intention of this review is to provide the basics of microwave energy applications
specific to biodiesel preparation and processing, preliminary understanding and explanation of microwave effect on the
chemical reactions (extraction and transesterification), update on process utilization and improvements, and informatio
related to different process configurations and reactor designs available for biodiesel production via microwave assisted
process and ultrasound assisted process

2: Production of biodiesel via microwave assisted process

Microwave energy based chemical synthesis has several merits and is important from both scientific and engineering
standpoints. Microwaves have been applied in numerous inorganic and organic chemical syntheses; perhaps, from the time
their ability to work as heat source was discovered. Recent laboratory scale microwave applications in biodiesel production
proved the potential of the technology to achieve superior results over conventional techniques. Short reaction time, cleaner
reaction products, and reduced separation-purification times are the key observations reported by many researchers. Energy
utilization and specific energy requirements for microwave based biodiesel synthesis are reportedly better than conventional
techniques. Microwaves can be very well utilized in feedstock preparation, extraction and transesterification stages of the
biodiesel production process. Although microwave technology has advanced in other food, pharmaceutical and polymer
chemistry related research and industry, it has yet to prove its potential in the biodiesel industry at large scale applications.
This paper reviews principles and practices of microwave energy technology as applied in biodiesel feedstock preparation and
processing. Analysis of laboratory scale studies, potential design and operation challenges for developing large scale biodiesel
production systems are discussed in detail.

Microwave heat transfer mechanism

Microwave heating mechanism is complex. The microwave method of heating can be illustrated as shown in Figure. A
comparison with conventional heating method would provide a base to compare the differences in heating mechanisms
and further realize the advantages associated with microwave heating.

3: Microwave role in biodiesel production:


Currently, commercial biodiesel production processes are based on either conventional or supercritical heating methods.
Commonly used methods are:

Pyrolysis,

Micro-emulsions,

Dilution

Transesterification of oils to esters


Among these methods, transesterification has proven to be the simplest and the most economical route to produce biodiesel,
with physical characteristics similar to fossil diesel and little or no deposit formation when used in diesel engines.
Transesterification of oils from any feedstock is to simply reduce the viscosity of the oils derived from them.
Transesterification is a process in which an alcohol (methanol or ethanol) in the presence of a catalyst
(acid or alkali or enzyme) is used to chemically break the molecule of the vegetable oils or animal fats into methyl
or ethyl esters of the renewable fuel.
The overall transesterification process is a sequence of three consecutive and reversible reactions, in which di and
monoglycerides are formed as intermediates, yielding one ester molecule in each step. The stoichiometric reaction requires
1 mole of a triglyceride and 3 moles of the alcohol. However, excess amount of alcohol is used to increase the yields
of the alkyl esters by shifting the equilibrium towards the formation of esters and to allow its phase separation from the
glycerol formed as a by-product. The product of transesterification process is known as biodiesel.
While transesterification of oils to produce biodiesel is a well-established method, there exist conversion and energy utilization
inefficiencies in the process which result in the high cost of biodiesel. These are mainly associated with the heating method
employed in the process.
Transesterification of organic feedstock to yield biodiesel can be performed by the following methods:

conventional heating with acid, base catalysts and co-solvents

sub- and super-critical methanol conditions with co-solvents and without catalyst

enzymatic method using lipases

microwave irradiation with acid, base and heterogeneous catalysts


Among these methods, conventional heating method requires longer reaction times with higher energy inputs and losses to the
ambient . Super and sub-critical methanol process operates in expensive reactors at high temperatures and pressures resulting in
higher energy inputs and higher production costs . The enzymatic method, though operates at much lower temperatures, requires
much longer reaction times . Microwave-assisted transesterification, on the other hand, is energy-efficient and quick process to
produce biodiesel from different feedstocks.

The production methods include pyrolysis, thermochemical liquefaction, supercritical reactors, oil and sand baths,
and jacket type heating. Ultrasound treatment was also favored in some processes. In recent years, many researchers
have tested application of microwaves in biodiesel production and optimization studies with various feedstocks.

Microwave energy, a non-conventional heating method is utilized in biodiesel production in two main stages:

oil extraction

chemicaltransesterification reaction.

It can be beneficial to combine the above two steps to perform a single-step extractive transesterification reaction as
discussed later. Biodiesel production involves mixing of appropriate ratios of oil, methanol (solvent) and catalysts as
shown in Figure.
The mixture is then processed through a microwave reactor followed by separation of products to yield biodiesel and glycer.

4 : Microwave based biodiesel production:

Microwave applications in biodiesel production can be separated based on different feedstock types. Many reports
include research on microwave-enhanced transesterification of

edible oils,

non-edible oils,

oils from algae and other cellulose based renewable feedstock.

4.1) Edible oils (first generation)


Rudolph diesel has first tested the engine by using the peanut oil and discovered that the vegetable oils can serve as
engine fuels after further treatment. Edible oils commonly used as feedstock for the biodiesel production have been
soybean, canola, corn, coconut, palm tree, rapeseed, rice bran, sunflower, safflower, camelina and cottonseed oils to just
name a few. Among these, soybean oil is the dominant feedstock and palm tree produces highest quantity of oils per
cultivated area [79,80]. Rapeseed and sunflower oils are predominant in the European Union. Although use of vegetable
oils to prepare biodiesel was well received in the early stage, soon it turned out be a food versus fuel issue.
This conflict arose due to increase in vegetable oil demands and prices.

4.2) Non-edible oils (second generation)


Among possible alternative biodiesel feedstocks are oils of non-edible crops such as jatropha, castor, neem, karanja, rubber
seed, used frying oils (waste cooking oil), animal fats, beef and sheep tallow. pongamiapinnata, maize, yellow grease,
poultry fat, castor, and Chinese tallow tree. While these feedstock do not conflict with food interest, they conflict with
other commercial products such as cosmetics and industrial products.

4.3) Algae and other feedstock (third generation)


Third generation biodiesel feedstock are those that do not conflict with any food, feed or cosmetic related human
consumption interests. Macro and microalgae, cyanobacteria, wastewater treatment plant activated sludge, switch
grass and other microbial communities belong to this type. Among these, algae seem to be a superior feedstock and offer
several advantages as follows:

1) Algae can utilize non-arable land;


2) oil content in algae is orders of magnitude higher than from other feedstocks such as corn, sugar cane, jatropha, etc.;
3) Algae need CO2 to photosynthesize and can be used to sequester CO2 from industrial sources of flue and flaring gas;
4) Algae-based fuels are carbon-neutral or even more carbon-capturing than releasing;
5) Algae can be used to remediate high-nutrient water sources such as sewage treatment plant and agricultural runoff;
6) End-products include biodiesel and/or other higher value feed (protein), pharmaceutical, and health-related products.
7) Different species of algae can be grown in polluted, saline, brackish, and freshwater;
8) Co-location of algal ponds with industrial production plants for potential recycling of CO2 and impaired waters.
Algal biofuels are thus renewable, sustainable, and environmentally-benign

5: Production of Biodiesel via Ultrasound assisted process


In biodiesel production, vigorous mixing is required to create sufficient contact between the vegetable oil/animal
fat and alcohol, especially at the beginning of the reaction.
Ultrasound is a useful tool to mix liquids that tend to separate. Ultrasonic waves cause intense mixing at micro-levels
and improve mass transfer greatly, so that the reaction can proceed at a much faster rate. Although not currently in wide
use, ultrasound is a promising technology for biodiesel production. Ultrasound processing results in similar yields of
biodiesel with a much shortened reaction time compared to the conventional stirred-tank procedure. Ultrasonic
reactors can process triglycerides into biodiesel within minutes. In addition, current users of the technology claim that
much less catalyst and methanol are required. Ultrasonic processing can be used successfully with a wide variety of
feedstocks, including high free fatty acid feedstocks. In addition, ethanol can be used instead of methanol. Catalysts
can include potassium and sodium hydroxide and sulfuric acid. Researchers have also reported using enzyme catalysts
with ultrasonic processing, and showed good results without much loss of enzymatic activity during the time of the study

5.1) How ultrasound work ?


Ultrasound refers to sound waves that are above the frequency for human hearing, which is approximately
20 kilohertz (kHz), or 20,000 cycles per second. These kinds of rapidly vibrating sound waves transfer energy into
the fluid and create violent vibrations, which form cavitation bubbles as the low pressure part of the sound passes
through the liquid. After the wave passes, the bubbles collapse, causing a sudden contraction of the fluid. This collapse
produces very intense mixing in the area of the bubbles. Such a high-energy action in the liquid can considerably
increase the reactivity of the reactant mixture and shorten the reaction time without involving elevated temperatures.
In fact, this reaction can be achieved at or slightly above ambient temperature. Ultrasound is characterized by its
frequency (kilohertz) as well as by its intensity (watts/cm2 ). A higher frequency causes the sonotrode to vibrate
faster, resulting in smaller cavitation bubbles and a larger surface area for mixing the alcohol and triglycerides.
Experiments have been done using frequencies ranging from 24 kHz to 1300 kHz, and biodiesel was successfully
produced within minutes in this range. If the intensity is increased, the amplitude of the vibration increases.
In other words, the probe travels farther back and forth with each cycle. This may increase the mixing effectiveness,
and it may also help the ultrasound waves travel farther into the liquid. More research is needed to determine
optimum levels of ultrasonication power input for biodiesel production. Using a higher frequency and intensity does
not necessarily increase the speed or effectiveness of the biodiesel reaction. Most experiments have used 20-24 kHz
for biodiesel processing. Because the ultrasonic waves are strongest within approximately a half inch of the probe
surface, some ultrasonic biodiesel reactors use a tube design, in which the liquids flow slowly and continuously
through a narrow tube fitted with a probe.

5.2) Ultrasound for Biodiesel Processing


Today, biodiesel is primarily produced in batch reactors. Ultrasound biodiesel processing allows for the continuous
inline processing.
Ultrasound can achieve a biodiesel yield in excess of 99%. Ultrasound reactors reduce the processing time from the
conventional 1 to 4 hour batch processing to less than 30 seconds. More important, ultrasound reduces the separation time
from 5 to 10 hours (using conventional agitation) to less than 60 minutes. The ultrasound does also help to decrease to
amount of catalyst required by up to 50% due to the increased chemical activity in the presence of cavitation. When using
ultrasound the amount of excess methanol required is reduced, too. Another benefit is the resulting increase in the purity
of the glycerin.

Ultrasound processing of biodiesel involves the following steps:

the vegetable oil or animal fat is being mixed with the methanol (which makes methyl esters) or ethanol (for ethyl esters) and
sodium or potassium methoxide or hydroxide

the mix is heated, e.g. to temperatures between 45 and 65degC

the heated mix is being sonicated inline for 5 to 15 seconds

glycerin drops out or is separated using centrifuges

the converted biodiesel is washed with water

Most commonly, the sonication is performed at an elevated pressure(1 to 3bar, gauge pressure) using a feed pump and an
adjustable back-pressure valve next to the flow cell.
Industrial biodiesel processing does not need much ultrasonic energy. The table above shows typical power requirements for
various flow rates. The actual energy requirement can be determined using a 1kW ultrasonic processor in bench-top scale. All
results from such bench-top trials can be scaled up easily. If required, FM and ATEX-certified ultrasonic devices are available,
such as the UIP1000-Exd.
Hielscher supplies industrial ultrasonic biodiesel processing equipment, worldwide. With ultrasonic processors of up to 16kW
power per single device, there is no limit in biodiesel plant size or processing capacity

6: How to convert oil to biodiesel Using Ultrasound assisted process?


Ultrasound can be used for the conversion of oil into biodiesel at any scale. The picture shows a small scale setup for the
processing of 60-70L (16 to 19 gallons). This is the typical setup for initial studies and process demonstration.

This setup consists of the following parts:

one 500 watts or 1,000 watts ultrasonic device (20kHz) with booster, sonotrode and flow cell
power meter for metering power and energy
80L processing tank (plastic, e.g. HDPE)
heating element (1 to 2kW)
10L catalyst premix tank (plastic, e.g. HDPE)
catalyst premixer (stirrer)
pump (centrifuge, mono or gear) for approx. 10 to 20L/min at 1 to 3 barg
back-pressure valve for adjusting pressure in the flow cell
pressure gauge for measuring feed pressure

Preparation
Potassium Hydroxide (0.2 to 0.4kg, catalyst) is being dissolved into approx. 8.5L Methanol in the catalyst pre-mix tank.
This requires stirring of the catalyst premix. The processing tank is being filled with 66L vegetable oil. The oil is being
heated by the heating element to 45 to 65degC.

Processing
When the catalyst is fully dissolved into the Methanol, the catalyst premix is mixed with the heated oil. The pump
feeds the mixture to the flow cell. By means of the back-pressure valve, the pressure is adjusted to 1 to 3barg
(15 to 45psig). Recirculation through the ultrasonic biodiesel reactor should performed for approx. 20 minutes.
During this time, the oil is being converted into biodiesel. After this, the pump and the ultrasound are switched off.
The glycerin (heavier phase) will separate from the biodiesel (lighter phase). The separation takes approx. 30 to
60 minutes. When the separation is finished, the glycerin can be drained.

7: Conclusions

Biodiesel can be produced with minimum environmental pollution by using low cost and renewable feedstock.
This paper illustrated methods for sustainable biodiesel production from various feedstock. Net energy benefit of the
biodiesel production process can be increased by using high oil yielding and low energy consuming feedstock
(low maintenance, low water consumption).
Biodiesel production costs can be reduced by utilizing locally available used cooking oils and by utilizing process
byproducts as raw materials in other chemical processes. Utilizing renewable feedstock such as algae will reduce the
environmental emissions and facilitate nutrient recovery and wastewater reuse and recycling.
Non-conventional technologies such as microwaves and ultrasonics have potential to reduce the energy footprint of the
biodiesel processes.

8: References

1 http://www.sciencedirect.com/science/article/pii/S2090123210000755
2 http://www.sustainablechemicalprocesses.com/content/pdf/2043-7129-1-5.pdf
3 http://www.hielscher.com/biodiesel_transesterification_01.htm
4 http://www3.aiche.org/proceedings/Abstract.aspx?PaperID=323655
5 http://www.scielo.br/scielo.php?pid=S0103-50532014000900025&script=sci_arttext
6 http://www.cese.uconn.edu/pdf/SUIB_Presentation.pdf
7 http://www.researchgate.net/publication/235716248_Thermal_analysis_on_the_process_of_microwaveassisted_biodiesel_production
8 http://www.researchgate.net/publication/49832078_Microwave-assisted_pyrolysis_of_microalgae_for_biofuel_production
9 http://www.academia.edu/11451680/Review_on_Biodiesel_Production_using_Process_Intensification_Techniques
10 http://www.sciencedirect.com/science/article/pii/S0960852411001246
11 http://www.researchgate.net/publication/26794971_Ultrasoundassisted_production_of_biodiesel_fuel_from_vegetable_oils_in_a_small_scale_circulation_process
12 http://www.sciencedirect.com/science/article/pii/S0960852409011328

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