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March 2011
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C&I Magazine
Microwave turns waste into watts
Patrick Walter,
07/03/2011
A new process that combines low
temperature pyrolysis with microwave
technology can turn almost any type
of biomass into chemicals and oils. The
inventors of the process say that farmers
may one day, in the future, band together
to buy one to turn agricultural waste,
such as straw, into a char that could be
burnt with coal. It could even be used to
turn waste paper into a useful fuel.
Biomass is of great interest to
researchers seeking to turn plant
material into chemicals or even transport
fuels, because there is potentially so
much of it available. A 2005 report from
the Oak Ridge National Laboratory, US,
estimated that approximately 1bn t of
dry biomass could be produced each
year in the US with relatively minor land
changes, while still meeting food and
feed demand.
Biomass encompasses more than
just traditional crops; it also includes
agricultural and forestry wastes, animal
dung and super-fast growing energy
crops like switchgrass and willow that
can be grown or marginal land with
fewer inputs. And unlike other plant
feedstocks used to produce chemicals
and fuels, such as maize, there is no food
versus fuel dilemma with these biomass
sources. However, scientists have been
stymied to date by the tough, woody
plant material, high in cellulose, which
is difficult to break into useful sugars.
The microwave pyrolysis process
being developed by chemists at the
University of York in the UK can get
around this problem and is able to
hydrolyse the cellulose in an energy
efficient manner. The process begins
with any type of cellulosic biomass
being heated in a reactor at around
180°C. Once the biomass has begun
to ‘soften’ it is then blasted with
microwave radiation, which causes
a decomposition chain reaction that
results in the production or sugars,
small molecules, oils and, eventually,
char.
The energy return on energy
invested is also good. The process gets
back 90% of the energy put into freeing
the sugars from the tough, cellulosic
materials. Preliminary results were
presented at the American Association
for the Advancement of Science annual
meeting held in Washington, DC, US,
on 16-21 February 2011.
James Clark, director of the
green chemistry centre of excellence
for industry at York, and one of the
inventors of the process, says: ‘Cellulose
is held together by rigid hydrogen
bonds, so presumably when it softens
there’s a bit of mobility there so the
microwaves can get in and trigger the
formation of protons and the protons
rapidly decompose the cellulose.’
He adds that this process is like acid
hydrolysis, a process that has been
investigated as a way of freeing the
sugars bound up in cellulose, without
the need to add acid. ‘We believe this
decomposition generates some sort of
reactive intermediate,’ Clark says. ‘These
reactive intermediates presumably kick
start the decomposition of everything
else there. So it’s not just that the
cellulose decomposes at 180°C.’
Clark says that once the microwave
processor gets working, the cellulose is
broken up into its constituent sugars.
These then undergo dehydration
reactions to produce levoglucosan, which
condenses to form longer chain, partially
functionalised carbon molecules. These
molecules then further condense to form
‘classic carbonaceous materials’, such as
oils, and, after longer processing, chars.
However, the oils that come out the
other end of the process are unlikely to
be able to be blended with fuels like
diesel or petrol straightaway. But Clark
says that there are some factors running
in their favour. ‘As your biomass is being
microwave activated, you’re producing
water and we continually take out the
water and that removes a lot of the small
polar molecules that are water soluble.
What that means, of course, is that the
oil you’ve got left is oxygen deficient,
which is great for transport fuels because
they don’t want oxygen: you want high
hydrogen, high carbon.’
The microwave processor
technology is currently being proven at
the green chemistry centre at York and
the team is now looking to commission
a pilot plant. They are in talks with
investors to build a continuous
processor at the UK government’s Food
and Environment Research Agency that
should be able to handle as much as
50kg of biomass per hour. Clark says
that this plant would give industry
a chance to see how the process
works and provide companies with
the opportunity to take away the end
products for further analysis.
These microwave processors,
which are likely to cost in the region
of £6m each, could also be very useful
for farmers looking to make more
money from agricultural residues.
By joining forces several farms could
buy a processor and turn farm waste,
such as straw, into a much higher
quality solid fuel. Clark says that
their char has a similar energy value
to coal and, as the process creates a
much denser end product, would be
much cheaper to transport.
In the UK, Drax, western Europe’s
biggest coal burning power plant,
began co-firing the station with a mix
of coal and biomass in 2003. Drax
says that this project should allow
it to produce 12.5% of its electricity
using co-firing, lowering its carbon
emissions. However, at the moment
it has proven difficult to keep Drax
supplied with enough good quality
biomass, Clark says. The processor
would give farmers the opportunity to
turn a waste product into a valuable
fuel that could generate power.
The team is currently working with
the UK’s Carbon Trust on ways to blend
these oils with transport fuels. This
is part of the Carbon Trust’s Pyrolysis
Challenge, which aims to replace a
large portion of transport fuels with
pyrolysis products.
To get around the problem of
blending, pyrolysis oils are likely to
require some catalytic upgrading.
This upgrading would cut the levels
of unsaturated compounds. ‘I think
there’s a good chance that we can
make intermediates which, with a
modest degree of catalytic upgrading,
will be blendable, because we’re
starting off in a good position with low
water and low oxygen,’ Clark says.
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