Dia 1 - Ghent University

Dia 1 - Ghent University

Testing the stability of a ZSM-5 catalyst under biomass fast pyrolysis conditions
Introduction

Experimental

Fast pyrolysis is a thermochemical process that contributes
to the conversion of biomass into a variety of fuels and
chemicals. It is defined as the rapid thermal decomposition
of matter in absence of oxygen and followed by a quick
condensation of the generated vapours. The target of this
process is to produce a liquid mixture of organic molecules
that is called pyrolysis oil or bio-oil, and which can be used
as feed for fuels and chemicals production. The objective of
the research carried out is to investigate the effects of a
repeatedly regenerated ZSM-5 catalyst (in total, eight
regeneration cycles) on the yields of the pyrolysis products in
relationship with the applied process conditions. The
changes in the performance of the successively regenerated
catalyst has been observed via detailed bio-oil (2D-GC/MS,
Karl-Fischer, MCRT), non-condensable gases (micro-GC)
and carbonaceous solids (elemental analyzer, BET SA)
analyses.

Materials:

Results

Pine wood with particle sizes between 1 and 2
mm was used as the feedstock. A commercial,
spray dried heterogeneous ZSM-5 based FCC
catalyst was used as the catalyst. Silica sand
with a mean diameter of 250 m and a particle
density of 2650 kg/m3 was used as the bed
material for non-catalytic experiments and
blended with the catalyst in case of the in-situ
catalytic and regeneration experiments. Twostage regeneration of the catalyst was
performed in an oven at 250 C and 600 C.

Equipment:
Experiments have been carried out in a fully
controlled, semi-continuously operated labscale set-up that enabled the production of biooil samples (ca. 50 g/run) suitable for a full
physicochemical characterization. A scheme of
the unit is shown in Fig. 1.

The effect of successive catalyst
regeneration on the product yields

The effect of successive catalyst regeneration on the
yields of non-condensable gas compounds

Fig. 2. The influence of successive catalyst regeneration (R1 to
R8, ) on the yields of products obtained in pyrolysis of pine
wood at 500 C. Results for the non-catalytic (NC, ) and
catalytic pyrolysis with fresh catalyst (R0, ) are included for
comparison.

Fig. 4. Catalytic pyrolysis of pine wood at 500C. Changes in (a) CO x yield (the sum of CO and
CO2), (b) CO/CO2 ratio, (c) CH4 yield, (d) C2+ yield (sum of C2H4, C2H6, C3H6 and C3H8) and (e)
H2 yield, obtained after successive reaction/regeneration cycles (R1 to R8, ). The result of noncatalytic (NC, ) and catalytic fast pyrolysis with fresh catalyst (R0, ) are included for
comparison.

The effect of successive catalyst
regeneration on the catalyst
Table 1. BET surface area of spent and
regenerated ZSM-5 based FCC catalysts, and
the normalized values, for catalytic pine wood
pyrolysis at 500 oC after subsequent catalyst
regenerations (R0 to R8).

Fig. 3. Changes in the coke-oncatalyst (heterogeneous coke)
yield along the successive
catalyst regeneration cycles
(R1 to R8, ) resulting from
experiments with pine wood at
500 C.

NC
R0
R1
R2
R3
R4
R5
R6
R7
R8

sand/catalyst
mix (m2/g)
9.9
7.6
10.9
9.2
6.8
8.1
6.7
3.5
3.8

Fig. 1. Scheme of
the pyrolysis set-up.

catalyst
(m2/g)
144.3
109.8
159.3
133.8
97.8
117.3
96.3
48.3
52.8

normalized
value, %
1.0
0.76
1.10
0.93
0.68
0.81
0.67
0.34
0.37

Conclusions
The trends in the pyrolysis product yields converging to that of noncatalytic levels were observed which revealed that the influence of the
catalyst slowly declined along the reaction/regeneration sequence. The
reason for this was that the catalyst tended to lose its activity along the
reaction/regeneration sequence. It can be explained by (1) deposition of
coke and tar on the catalyst (Fig. 3 and Table 1) (2) the change in the
physical, chemical and thermal properties of the catalyst (e.g.
poisoning,
fouling,
attrition,
steaming)
after
several
reaction/regeneration cycles and (3) the accumulation of ash in the
regenerated bed material which has two effects; favouring secondary
cracking reactions and blocking active pores of the catalyst.

Guray Yildiza*, Tom Lathouwersa, Hilal Ezgi Toramanb, Kevin M. van Geemb, Frederik Ronssea,
Ruben van Durenc, Sascha R. A. Kerstend, Wolter Prinsa
Department of Biosystems Engineering, Ghent University, Coupure Links 653, B-9000, Ghent, Belgium
b
Laboratory for Chemical Technology (LCT), Ghent University, Technologiepark 918, B-9052 Ghent, Belgium
c
Albemarle Catalysts Company BV, Nieuwendammerkade 13, P.O. Box 37650, 1030 BE Amsterdam, The Netherlands
d
Sustainable Process Technology Group, Faculty of Science and Technology, University of Twente,
Postbus 217, 7500AE Enschede, The Netherlands
a

* Tel.: +32(0)9264 6190; e-mail: [email protected]

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