Fluidized bed pyrolysis of lignin in a bubbling bed
reactor
Pietro Palmisano(*), Valentina Lago, Franco Berruti, Cedric Briens
Institute for Chemicals and Fuels from Alternative Resources
University of Western Ontario
Bio-Energy Conference III
Canary Islands-Spain
May 22-27, 2011
*: [email protected]
What is lignin?
Lignin is a complex
chemical compound
chemical most
commonly derived from
wood (now considered a
sort of by-product for
the production of
cellulose).
It is the most important
natural polymer actually
used like fuel, could be
used as chemicals source
(alternative to the crude
oil), for this reason there
are many research
project in the world
about its cracking.
Flash Pyrolysis:
Conversion of Biomass into Bio-oil and Bio-char
HEAT
10-40%
Gases
20-80%
Biomass Liquid Bio-oil
e.g. lignin Bubbling Bed Pyrolyzer
10-50%
Temperature: 300-600 °C
Solid Char
Experimental Apparatus: Continuous System
Heated line
Reactor
Gas
sampling
Solid feeder Condensing zone
N2 fluidization
4
Solid dumping
Experimental Apparatus: Continuous System Feeding
N2 Pulse
N2 continuous
5
Pyrolysis Reactor and Operating Parameters in
Continuous System
Vapour residence time = 2 s Bio-oil vapours and
Reactor section = 7.5 cm
gases
Reactor volume = 2.8 liters
Hot filter traps fine char particles
Sand weight = 1.5 kg
Sand dpsm = 180 µm
Biomass injection rate = 1 kg/hr
The char stays
in the bed
Biomass injection
6 N2 or Recycled pyrolysis permanent gases
Experimental Results Continuous System:
Feeding line: bottom or freeboard?
Vapour Residence time =2 s
Temperature=500˚C-650˚C
Vapours
Lignin foam
Lignin
Fluidized sand
Fluidized sand
Lignin
Reactor and feeding line plugged after With this setup, 200g of lignin fed in 12
few pulses of lignin injection minutes.
7
Test run with freeboard feeding
SOLID, LIQUID AND GAS YIELD
60
50
48%
40
% 30 liquid yield
20 solid yield
gas yield
10
0
500 550 600 650
Temperature [°C]
Test run with freeboard feeding
ENERGY CONVERSION LIGNIN LHV= 26 kJ/g
60
50
40
% 30 E.C. oil
E.C. char
20 E.C. gas
10
0
500 550 600 650
Temperature [°C]
Test run with freeboard feeding
WATER CONTENT
30
[%]
25
Water / tot bio-oil
26.14 25.47
bio
20 21.81 22.21
12.25 13.28
15 11.39 11.10
10 WATER CONTENT
PYROLYSIS
5 WATER
0
500 550 600 650
Temperature [°C]
Test run with freeboard feeding
CARBON CONTENT
60
52.95
55
50
45.52
% 45 41.87
bio-oil
40 38.18
bio-char
33.53 34.20 34.51
35 32.03
30
500 550 600 650
Temperature [°C]
TEST RUNS WITH FREEBOARD FEEDING
H/C MOLAR RATIO
10
8.90 9.19 9.50
8 8.56
mol/mol
6 5.17
4.35
3.63
4 3.03 Bio-oil
Bio-char
2
0
500 550 600 650
Temperature [°C]
Problems with continuous system
• Lignin starts melting at low temperature:
– Even the pulsed feeder plugs
– Hinders contact between hot sand and lignin particles: pyrolysis is not very fast
• Low density lignin foam:
– Floats on top of the bed and plugs reactor
– Hinders fast heat transfer to reacting lignin: pyrolysis is not very fast
→ Could not produce large amounts of lignin bio-oil
Lignin injected = 200 g in 12 minutes in the freeboard
Bio-char presents a solid sponge form
Density of char = 0.20 g/cm3
Density of lignin = 0.33 g/cm3
Batch System:
Mechanical Fluidized Reactor
MFR: BATCH SYSTEM
Vapours
T= 25-500 oC in 2 h
No gas fluidization
Mechanical mixing destroys the
No foam after reaction lignin sponge, promoting good
contact between FCC and char.
Reactor volume: 3 liters
Lignin / (inert bed particles) = The MFR would not be easy to
1/5 wt/wt scale up.
Solutions for continuous system
Solutions that could be implemented in scaled-up units:
• Lignin starts melting at low temperature:
→ changed feeding pipe location:
- above the bed and inclined downward
→ lignin has to be injected down into the bed
→ Feeding pipe jacketed for cooling
• Low density lignin foam:
→ Supersonic attrition jets break up the foam
→ Jets swirl the bed to enhance heat transfer
Continuous System Implementation:
cooled feeding line, internal swirling attrition jet
Reactor cap
Swirling attrition jets
Filter
Lignin
Attrition jets
External jacket for cooling (using H2O)
The lignin can be easily fed in the bubbling bed, the
temperature of the feeding line is below 200˚C
New Continuous System: Preliminary results
Biomass injected = 200 g (bio-oil and biochar collected) over 1.5 kg of sand
Feeding (cooled) line: ok
Bio-char foam partially destroyed
The swirling attrition jets provide good mixing but could not completely destroy the
foam
Fine biochar particles are well mixed with the sand
Continuous reactor with Continuous reactor
swirling attrition jet without attrition jet
Sand samples
A B
17
New Continuous System:
Effect of the char concentration vs Yields
Temperature operation : 500˚C
Vapour residence time 1sec
Lignin fed for each run: 100g
If the char concentration
increases its value into the
fluidized bed,
we will achieve lower gas
and liquid yields (keeping
%
constant temperature and
vapour residence time)
higher solid yields.
“char makes char”
Char concentration in the bed [%]
Conclusions and future works:
The Lignin pyrolysis using a bubbling bed reactor has been studied and
experimented in several projects with not good results. The present work can
suggest some solutions about a pilot plant, interesting in a future scaling up.
FEEDING LINE:
Feeding line in the freeboard (achieving a poor mixing with the hot sand) but
biochar sponge foam formation.
Cooled and inclined feeding line at the bottom (good mixing, but not
enough, with the hot sand)
IMPROVEMENT for MIXING and CHAR DESTRUCTION:
To achieve a good and strong interaction among sand, lignin and char, it is
necessary to increase the force that the hot sand has to get the solid biochar
particle destroyng (lighter than the sand, so floating above it during
fluidization). In a batch system (mechanical fluidized reactor) the mechanical
blades’ agitator had enough force to destroy them reaching a good mixing. In
order to have the same results, a swirling (internal) multiple attrition jets have
been adopted, and it was partially able to destroy part of the sponge foam
solid char. Solution that is even easily scalable up. In this case is strictly
necessary the feeding line in the bottom of the bed (with a cooled system).
Thanks for your kind attention
