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introduction
need to find clean, efficient ways to perform
chemistry
atom economy
improved product yields
renewable feedstocks
energy efficiency
new chemistry
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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introduction
as a tool for preparative chemistry, microwave
heating has a number of advantages
reactions complete in minutes instead of hours
yields can be improved
less by-product formation
new chemistry
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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physical chemistry concepts
only four permitted frequencies for industrial,
medical and scientific use of microwaves
915 MHz
2450 MHz (2.45 GHz)
5800 MHz (5.80 GHz)
27120 MHz (27.12 GHz)
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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X-rays
physical chemistry concepts
ultraviolet infrared microwaves
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 1
3x1012 3x1010 3x108 3x106 3x104 3x102
frequency (MHz)
wavelength (m)
molecular rotations
molecular vibrations
outer-shellelectrons
inner-shell
electrons
radiowavesvisible
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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physical chemistry concepts
conventional heating by conduction
convection currents
temperature on the outside surface is greater than that of the contents
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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physical chemistry concepts
microwave irradiation results in direct heating of
reagents and / or solvents
microwave heating conventional heating
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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new synthetic methods group
expand microwave technologies and methodologies so thatmicrowave energy becomes the primary tool for scientists in
any situation where heating and/or long reaction times are
involved
http://homepages.uconn.edu/~nil03002/index.html
research group
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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new synthetic methods group
biologicalchemistry
emergingareas
inorganicsynthesis
organicsynthesis
microwaveirradiation
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
research group
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alternatives to petroleum-based fuels have
to be found
biodiesel as an alternative to fossil fuel
replacement of diesel fuel by biodiesel is something that is immediately
applicable
biofuels represent abundant carbon-neutral renewable resources for the
production of bioenergy
with little modification, diesel engine vehicles can use biodiesel
can also be used as heating oil
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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+ MeOHcatalyst
glycerin biodieselvegetable oil
O
ROO
ROO
RO
OH
OH
OH
+
O
OMeR
stoichiometric ratio is 1 : 3 ratios of 1 : 9 1 : 30 usually used
preparation of biodiesel
biodiesels are the simple alkyl esters of fatty acids
generally prepared by vegetable oil by transesterification with methanol
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
accelerating the biofuels revolution
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preparation of biodiesel
preparation of biodiesel
most commonly used catalysts are NaOH, KOH and H2SO4starting oil and methanol are generally heated to near reflux and stirred with the catalyst
in the case of the basic catalysts, the base is dissolved in the methanol prior to addition
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
accelerating the biofuels revolution
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can biodiesel be made using microwave heating?
literature survey
one report of the use of a domestic microwave for reaction between methanol
and seed oils (J. MW Power Elecromag. Energy 1999, 34, 3)
scientific microwave apparatus has been used for transesterification of
triglycerides to fatty acid methyl esters and involves a zeolite catalyst,
heating to 170 C for 2 h in a sealed vessel and only moderate conversions
are obtained (C. R. Chemie, 2004, 7, 601)
three patent applications have been filed - involve use of specially designedapparatus (WO 03/014272 A2, US 0274065 A1, US 0162245 A1)
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
starting on a small scale in a 125 mL open vessel
accelerating the biofuels revolution
+ MeOH10 g oil quantitative conversion to biodiesel5 wt % KOH
MW
oil to methanol ratio of 1 : 6 heat to 50 C and hold for 1 min
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
scaling up the reaction
using a 1 : 6 oil to methanol ratio and 1 wt% KOH the reaction mixture is heated to 50 C
and held at this temperature for 1 min
quantitative conversion to biodiesel
can be performed on scales up to 3 kg (~3.5 L) of oil
Fast easy preparation of biodiesel using microwave heating
Leadbeater N. E.; Stencel, L. M.Energy Fuels, 2006, 20, 2281-2283
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
scaling up the reaction
used vegetable oil can be processed
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
modification for continuous-flow processing at atmospheric pressure
use a 2 L reaction vessel
stirbar
product removal line
raw materials input line
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
modification for continuous-flow processing in a 2 L vessel
feedstock is pumped through the vessel at a flow rates of 1 -2 L / min
microwave unit is working at ~80 % of power output
at this rate, material is in the microwave cavity for 1-2 min
still maintain very high levels of product conversion
Continuous-Flow Preparation of Biodiesel Using Microwave Heating Barnard, T. M.; Leadbeater, N. E.;
Boucher, M. B.; Stencel, L. M.; Wilhite, B. A.Energy Fuels, 2007, 21, 1777-1783
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
modification for continuous-flow processing at atmospheric pressure
a 4 L vessel is about the largest possible before issues arise with penetration depth
accelerating the biofuels revolution
microwaves for biodiesel production:
accelerating the biofuels revolutionUCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
towards a simpler, faster, more efficient modular design
modification for continuous-flow processing in a 4 L vessel
feedstock is pumped through the vessel at a flow rates of ~ 7 L / min (~110 gallons / hr)
microwave unit is working continuously at 100 % of power output
at this rate, material is in the microwave cavity for less than 1 min
still maintain very high levels of product conversion
Continuous-Flow Preparation of Biodiesel Using Microwave Heating Barnard, T. M.; Leadbeater, N. E.;
Boucher, M. B.; Stencel, L. M.; Wilhite, B. A.Energy Fuels, 2007, 21, 1777-1783
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
energy efficiency of the process: conventional heating
data for conventional routes reported in the 1998 joint USDA / DOE study
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
energy efficiency of the process: microwave heating
the microwave is working at 100 % of the maximum power output
the magnetron is not 100 % efficient
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
energy efficiency of the process: comparison
accelerating the biofuels revolution
conventional heating 94.3 kJ / L
microwave, continuous-flow at 7.2 L / min feedstock flow 26.0 kJ / L
microwave, continuous-flow at 2 L / min feedstock flow 60.3 kJ / L
microwave heating, 4.6 L batch reaction 90.1 kJ / L
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
single unit applications
small biodiesel manufacturer
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
single unit applications
small biodiesel manufacturer
cooperative of biodiesel manufacturers
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
single unit applications
small biodiesel manufacturer
cooperative of biodiesel manufacturers
biodiesel for heating oil
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
multiple units in parallel
offers high throughput still with a small footprint
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
multiple units in parallel
offers high throughput still with a small footprint
offers redundancy
accelerating the biofuels revolution
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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can biodiesel be made using microwave heating?
latest results
acid catalyzed methodology has been developed
butanol can be used as a feedstock
accelerating the biofuels revolution
Batch and continuous-flow preparation of biodiesel derived from butanol and facilitated by microwave heating
Barnard, T. M.; Leadbeater, N. E.; Stencel, L. M.;Energy Fuels, 2008,in press
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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microwave heating offers a viable approach to
biodiesel production
the methodology is fast and easy
acid- and base-catalyzed routes are possible
microwave unit has a small footprint but high throughput
calculations show that the microwave methodology is efficient
future is exciting and will bring many new opportunities
summary
microwaves for biodiesel production:accelerating the biofuels revolution
UCONN Sustainable Energy Symposium, March 31, 2008
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acknowledgements
T. Michael Barnard
Lauren Stencel
Matthew Boucher
Benjamin Wilhite
University of Connecticut Research Fund
NSF-REU program
CEM Microwave Technology
acknowledgements
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acknowledgementsWEBSITE http://chemistry.uconn.edu/leadbeater.html
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