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

*: ppalmisa@uwo.ca
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
No foam after reaction
Reactor volume: 3 liters
Lignin / (inert bed particles) =
1/5 wt/wt

Mechanical mixing destroys the
lignin sponge, promoting good
contact between FCC and char.

The MFR would not be easy to
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