Applied Catalysis A: General 376 (2010) 56–65

Contents lists available at ScienceDirect

Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Attrition resistance of a VPO catalyst

A. Thon, J. Werther *
Institute of Solids Process Engineering and Particle Technology, Hamburg University of Technology, Denickestrasse 15, D-21073 Hamburg, Germany

A R T I C L E I N F O A B S T R A C T

Article history: The attrition propensity of used and fresh vanadium phosphorous oxide (VPO) catalyst subjected to
Received 31 July 2009 mechanical stress in a gas cyclone and in a bubbling-fluidized bed with and without submerged gas jet
Received in revised form 24 November 2009 has been investigated. Attrition models for the investigated sources of attrition have been adopted from
Accepted 25 November 2009
literature. The attrition tests confirmed the relationship between the operating conditions and the
Available online 1 December 2009
steady-state attrition rates under abrasion conditions. The material specific attrition rate constants for
the three sources of attrition have been determined. These constants were compared with those
Keywords:
measured for other catalyst materials in previous attrition tests. It is found, that the investigated VPO
Attrition
catalyst has a low attrition propensity comparable to FCC-catalyst, when subjected to mechanical stress
Abrasion
Cyclone in gas cyclone and in fluidized bed with submerged gas jet. The attrition rate constant of the VPO catalyst
Fluidized bed subjected to mechanical stress in the bubbling-fluidized bed seems to be slightly higher than those
VPO catalyst measured for FCC-catalysts. However, the deviation is in the range of the experimental error. In
agreement with previous findings for other catalysts the cyclone attrition rate constant for fresh VPO
catalyst is higher than for used catalyst.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction available data for attrition characteristics of a range of fluidized

In any fluidized bed process – may it be a combustor, dryer or
chemical reactor – the bed material is in vigorous motion and
thus inevitably subjected to mechanical stress due to inter-
particle collisions and bed-to-wall impacts. This mechanical
stress leads to a gradual degradation of the individual bed
particles, which is quite often an unwanted phenomenon that is
therefore termed ‘‘attrition’’. The consequence of attrition in
fluidized bed processes is the generation of fines that cannot be
kept inside the system. Hence attrition creates an additional
burden on the filtration systems, i.e. the collection systems must
be larger [1,2], and most importantly a loss of valuable material
[3].
In the development of DuPont’s maleic anhydride process [3]
the attrition resistance of the catalyst was a key issue. In the
present work the attrition propensity of DuPont’s VPO catalyst
has been investigated by attrition tests under well-defined
conditions in a gas cyclone, in a bubbling-fluidized bed and in a
bubbling-fluidized bed with a submerged gas jet. For each of the
different stress mechanisms attrition rate constants were
calculated. The resulting parameter values were compared with
Abbreviations: FCC, fluidized cracking catalyst; PSD, particle size distribution; SEM,
scanning electron microscope; VPO, vanadium phosphorous oxide.
* Corresponding author. Tel.: +49 40 42878 3039; fax: +49 40 42878 2678.
E-mail address: werther@tuhh.de (J. Werther).
bed materials.
2. State of the art of attrition characterization
In general, the mode of attrition may vary from pure abrasion
to total fragmentation of the particles [4,5]. Abrasion implies
that exclusively asperities are removed from the particle’s
surfaces. It thus produces a lot of elutriable fines, whereas the
particle size distribution of the mother particles is hardly
changed. In contrast to this, fragmentation is a process of
particle breakage into similarly sized pieces. As a result of
fragmentation, the number of particles increases and the
particle size distribution becomes significantly broader with a
distinctly smaller mean diameter compared to the original one.
Therefore the main criterion for the distinction between
abrasion and fragmentation is the characteristic change in the
particle size distribution of the material [6].
Various factors have been identified to affect the extent or
mode of attrition. They can be classified in two groups, namely
the material properties and the process conditions [7]. Material
properties affecting the attrition are for example the composi-
tion, the size, the shape and the surface structure of the particle.
Process conditions such as gas and solid velocities or wall
hardness, generate the mechanical stress leading to attrition of
the solid particles. The assessment of the material’s strength is
based on so called attrition tests, in which a single particle or a
bulk sample of the material is to a certain extent subjected to a

0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.11.036
 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65 57

as particle breakage, no distinction between abrasion and

Nomenclature breakage-produced fine particles can be made. Hence, insights
into these attrition mechanisms may be obtained from the
Ac,in cross-sectional area of the cyclone inlet (m2) observation of the change in the particle size distribution as
Cb attrition rate constant for bubble-induced attrition, mentioned above.
def. by Eq. (2) (1/m) Even though many works deal with bubble-induced attrition,
the attrition mechanisms are not quite clear yet [7]. Ray et al.
Cc particle size-independent cyclone attrition rate
[10] proposed a surface-reaction model to simulate the
constant, def. by Eq. (5) (s2/m3)
distribution of attrition rates in a multi component mixture.
Cj particle size-independent jet attrition rate con-
The attrition rate of each component depends on its surface area.
stant, def. by Eq. (3) (s2/m3) In the limiting case of a minute fraction of attainable material in
dor diameter of the orifice (m) a bed of non-attainable ones the attrition rate of the particles is
dp mean particle size (m) inversely proportional to the average particle size. This is the
mb actual bed mass (kg) case of coal char in a bed of sand in a fluidized bed combustor
ṁc;in mass flux into the cyclone (kg/s) [11]. On the contrary the attrition rate of the material with the
mfilter mass collected on the filters down stream of the dominant fraction of surface area is almost independent of the
cyclone overflow (kg) average particle size [10]. This is in agreement with the studies
mloss elutriated mass (kg) by Merrick and Highly [1] and Pis et al. [12] who found that the
attrition rate is independent of the particle size. In the present
ṁloss mass flux in the cyclone loss due to abrasion (kg/s)
study a single component material is used and the attrition rate
msolid feed total mass passed through the cyclone (kg)
is therefore not influenced by the average particle size.
n number of samples (–) It is generally agreed that the bubble-induced attrition rate rb
nor number of orifices in a multihole gas distributor (–) is influenced by the excess gas velocity (u  umin) [7]. The
rb bubble-induced attrition rate, def. by Eq. (2) (1/s) velocity umin is the threshold velocity above which the bubble-
rc cyclone attrition rate per pass through the cyclone, induced attrition occurs. Its value varies from umin = umf to
def. by Eq. (5) (–) umin  umf. According to Merrick and Highley [1], Arena et al.
Rj jet attrition rate, def. by Eq. (3) (kg/s) [13] and Pis et al. [12] the bubble-induced attrition is directly
rtot attrition rate (1/s) proportional to the excess gas velocity. The attrition rate is
s standard deviation of n samples (–) calculated according to [1]
u gas velocity based on the bed’s empty cross-section
1 dmloss
(m/s) rb ¼ ¼ C b  ðu  umin Þ (2)
mb dt
umf minimum fluidization velocity (m/s)
umin threshold velocity, def. by Eq. (2) (m/s) In Eq. (2) Cb is the material specific steady-state attrition rate
uc gas velocity at the cyclone inlet (m/s) constant for bubble-induced attrition.
xi value of a single sample (–) According to Werther and Xi [14] the parameters influencing
x mean value of the samples (–) the jet-induced attrition rate are the mean particle size dp, the
diameter of the orifice dor and the jet gas velocity uor. The jet
Greek letters attrition rate at steady-state conditions is given by Werther and
mc solids loading at cyclone inlet (–) Reppenhagen [7]
rg gas density (kg/m3)
dmloss
Rj ¼ ¼ nor  C j  dp  rg  d2or  u3or (3)
dt
specific stress. The attrition propensity of a given material
strongly depends on the type of stress to which it is subjected to In Eq. (3) Cj is the particle size-independent material specific
[5], hence it is required to simulate the process stress in order to steady-state jet attrition rate constant and nor is the number of
relate the attrition test results with the attrition in the specific orifices e.g. in the bottom plate from which jets are issuing.
process. The attrition in the cyclone occurs while particles pass through
In a fluidized bed system several sources of attrition can be the cyclone. Therefore the attrition rate is not related to the bed
identified, e.g. attrition by gas jets issuing into the fluidized bed, mass mb but to the solid mass flow into the cyclone ṁc;in . The
attrition due to bubble-induced solids motion and attrition in the cyclone attrition rate rc is then given by
cyclones (e.g. [8,9]). In order to assess the particular attrition rates
it is necessary to consider those sources separately. 1 dmloss
rc ¼ (4)
In fluidized bed experiments most authors consider the ṁc;in dt
attrition-induced material loss only, i.e. they assume that all
attrition products are elutriated. Consequently the elutriated mass The main process parameters influencing the cyclone attrition rate
of particles is measured. The results are commonly expressed by an are according to Reppenhagen and Werther [7] the solids loading
attrition rate rtot, which is defined as the time-depending relative at the cyclone entry mc, the gas velocity at the cyclone inlet uc and
change in elutriated mass mloss based on the actual bed mass mb, the mean particle size dp. The steady-state cyclone attrition rate is
given by
1 dmloss
r tot ¼ (1) 1 dmloss
mb dt rc ¼ ¼ C c  dp  u2c  mc 0;5 (5)
ṁc;in dt
The above definition of the attrition rate is not taking breakage
events or shrinking of the mother particles into account. Under with Cc as the material specific particle size-independent steady-
process condition with particle stress resulting in abrasion as well state cyclone attrition rate constant.
58 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65

Fig. 2. Experimental set-up for attrition tests in cyclone.

3.2. Measurement of attrition in a fluidized bed with submerged gas jet

The jet-induced attrition of the VPO material is investigated

Fig. 1. Experimental set-up for attrition tests in fluidized bed.
3. Experimental
3.1. Measurement of bubble-induced attrition
The tests of the effect of bubble-induced attrition were
carried out in a stainless steel lab-scale column with an inner
diameter of 50 mm and a height of 1 m. The gas distributor was
a porous plate. A gravity separator, 150 mm ID and 0.3 m high
was mounted on top of the fluidization column (Fig. 1).
The off-gas was sent through two filters arranged in parallel.
The alternate use of these filters enabled time-resolved capture of
elutriated fines at the exhaust. The mass of produced fines was
measured by the weight change of the filters.
The air flow is controlled by mass flow controllers. The inlet gas
velocity based on the bed’s empty cross-section can be varied from
0 to 1 m/s. The particle size distribution of the bed material is
measured before and after attrition tests.
using the atmospheric fluidized bed described in Section 3.1
combined with a special gas distributor. This gas distributor is a
porous plate with one nozzle integrated in the centre. The nozzle
has an inner diameter of 2 mm. The volume flow through the
porous part of the gas distributor and the nozzle can be adjusted
independently by two mass flow controllers. The jet gas velocity in
the nozzle was 100 and 50 m/s. The volume flow through the
porous part of the gas distributor was 4.7 and 2.4 l/min, which
respectively led to gas velocities based on the bed’s empty cross-
section of 0.2 and 0.1 m/s. The mass of the bed material used for the
jet attrition test was 450 and 380 g, respectively. The mass of
produced fines is measured according to Section 3.1 by means of
the weight change of the filters.
3.3. Measurement of attrition occurring in the cyclone
The experimental setup developed by Reppenhagen and
Werther [15] was used (Fig. 2).
The experiments were conducted in a P5/6-30 cyclone (the
dimensions are given in Ref. [15]).

Table 1

mc uc Mass flow Total solid mass rc of used VPO Mean value rc of fresh VPO Mean value
[kg/kg] [m/s] [g/s] [kg] 106 [kg/kg] 106 [kg/kg] 106 [kg/kg] 106 [kg/kg]

0.5 15 4.28 0.77 10.4  1.7 10.5  2.1 48.4  2.3 48.6
13.9  2.8 48.7  4.2
11.0  1.2 –
7.9  2.0 –
10.9  1.8 –
8.7  1.8 –
0.5 20 5.71 1.03 27.8  2.6 21.3  4.8 128.1  9.1 127.4
16.2  1.8 126.7  4.6
19.8  1.7 –
21.3  7.7 –
0.5 25 7.14 1.28 55.8  6.9 57.7 238.5  13.1 238.5
59.5  8.9 -
0.1 20 1.14 0.21 93.4  6.8 93.0 271.3  22.6 271.3
92.5  7.7 –
1.0 20 11.42 2.06 14.1  1.6 14.1 86.9  1.7 86.9
1.5 20 17,13 3.08 11.7  1.7 11.7 55.2  6.9 55.2
2.0 20 22.84 4.11 5.7  0.9 5.7 51.6  12.0 51.6

In the first columns the operating conditions for the cyclone attrition tests are shown. In the next column the measured steady-state attrition rates  the standard deviation for
each cyclone attrition tests with used and fresh VPO are given. In the following column the mean steady-state attrition rates for the operating conditions calculated from the results
of the individual experiments are shown.
 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65
The basic idea of measuring the cyclone attrition rate is to pass a
batch of particles several times through an isolated cyclone and to
measure the cyclone loss. The cyclone catch and cyclone loss are
not mixed. The cyclone is operated in a suction mode which makes
it possible to introduce the solids via a vibrating feeder into a tube
attached to the cyclone inlet. The separate feeding of the solids
allows an independent variation of gas inlet velocity uc and solids
loading at the entrance of the cyclone mc. The gas flow rate is
measured by a rotameter and can be adjusted via a manual valve.
The inlet mass flow of solids ṁc;in is controlled by the vibration
feeder.
The solid loading mc at the entrance of the cyclone is defined as
the ratio of solids mass flow per gas mass flow and is calculated
according to [15]
ṁc;in
mc ¼
rg  uc  Ac;in
where Ac,in is the cross-sectional area of the cyclone inlet and rg is
the gas density, respectively.
After each pass through the cyclone the material collected in the
underflow hopper is used as feed material for the next run by
simply exchanging the hoppers of underflow and feed. The cyclone
overflow is connected to a filter. The filter is intended to collect the
abrasion-produced fine particles. The amount of abrasion-pro-
duced fines is measured by the increase in weight of the filter. In
order to investigate whether the process conditions lead to pure
abrasion or to abrasion and particle breakage, the particle size
distribution of the cyclone catch is considered. Therefore samples
of the cyclone catch are taken from the underflow hopper. To
minimize the sampling error a sample splitter is used.
3.4. Materials used for attrition tests
In this study two different vanadium phosphorous oxide (VPO)
materials were used for attrition tests. The samples were received
from the École Polytechnique de Montréal in the framework of the
International VPO Workshop. One of the VPO catalyst samples has
been used in the technical process. This sample is called used ‘‘u’’
VPO. The other sample is fresh ‘‘f’’ material which has not been
used in the process previously.
For preliminary characterization the particle size distribution of
both materials was measured by laser diffraction with the LS
13320 Beckman Coulter. Since particle attrition is strongly affected
by particle properties such as surface structure and shape,
scanning electron microscope (SEM) images of both materials
were made using a Jeol JSM-840A with a tungsten cathode.
Preliminary fluidization experiments were performed to
determine the minimum fluidization velocity of the materials.
The pressure drop over the bed was measured for different gas
velocities using a cylindrical bed of 100 mm inner diameter with
batches of 860 g of catalyst.
Fig. 4. (a) SEM image of used VPO particles before attrition test; (b) and (c) SEM image of fresh VPO particles before attrition test.
59
Fig. 3. Mass particle size distributions of used and fresh VPO material before
attrition tests.
(6)
4. Results and Discussion
4.1. Characterization of the materials
The initial particle size distribution (PSD) of the used and fresh
VPO materials was measured (Fig. 3).
The particle size distributions of both materials start below
5 mm. The comparison of the PSDs measured for fresh and used
VPO material shows, that the former one is slightly broader. These
differences in the particle size distribution may be attributed to
abrasion and breakage due to the stress the used sample has been
subjected to in the process. The surface mean diameters of the used
and fresh VPO material are 49 and 57 mm, respectively. Since the
particle size distribution is narrow the material is used in the
experiments without separating it into different size fractions. The
surface mean diameter is used for the characterization of the bulk
material’s particle size.
SEM images of the particles before they are used in attrition
tests are shown in Fig. 4.
A comparison of the images of the used (Fig. 4a) and fresh
(Fig. 4b and c) VPO material shows, that the surface of the used VPO
particles is smoother and the particles are more spherical
compared to those in the fresh VPO material. In Fig. 5 broken
VPO particles are shown.
The particles consist of an outer shell and an inner porous
structure. The SiO2-rich surface layer of the VPO catalyst is
supposed to absorb the mechanical stress, since the inner structure
is less attrition-resistant [16].
The measured minimum fluidization velocity of used VPO is
0.27 cm/s. It is calculated using the pressure drop versus superficial
gas velocity profile measured in the preliminary fluidization
experiment. No significantly differing value was determined for
the fresh catalyst.
60 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65
Fig. 5. (a) SEM image of a broken fresh VPO particle before attrition test; (b) SEM image of a broken used VPO particle after attrition test.
4.2. Attrition occurring in cyclone
The cyclone attrition rate for each pass through the cyclone is
calculated by the mass of elutriated fine particles collected on the
filter.
1 dmloss Dmfilter
rc ¼ ¼ (7)
ṁc;in dt msolidfeed
The cyclone attrition rates rc versus the number of passes through
the cyclone are shown in Fig. 6.
The attrition rates measured in tests with used VPO catalyst
decrease within the first passes through the cyclone and finally
reach a steady-state value. The slightly higher attrition rates
measured in the first runs result from a sifting of the feed material.
Fine particles present in the feed material will be elutriated
together with attrition-produced fine particles. In contrast to this
the fresh VPO exhibits a slight increase in the attrition rate within
the first passes through the cyclone. This increase can be explained
by the fragmentation of weak particles present in the fresh VPO
material. The breakage of primary regular particles generates
angular shaped particles (Fig. 5) which are inherently more
susceptible to further attrition. Moreover the structure of the VPO
catalyst (Section 4.1) might enhance this effect, because after
fragmentation the porous core could be subjected to mechanical
stress.
To investigate whether 15 passes through the cyclone are
sufficient to reach steady-state conditions attrition rates of
experiments with 25 passes through the cyclone were compared
with those of tests with 15 passes (Fig. 6). It can be seen, that after
Fig. 6. Attrition rates plotted versus the number of passes through the cyclone for
operating conditions uc = 20 m/s and mc = 0.5 kg/kg; two experiments with fresh ‘‘f’’
and three experiments with used ‘‘u’’ VPO.
approximately 6–8 passes through the cyclone the attrition rate
becomes independent of the number of passes through the
cyclone.
In the standard cyclone attrition test the sample was passed 15
times through the cyclone. The gas inlet velocity uc and the solids
loading at the entry of the cyclone mc were varied from 15 to 25 m/
s and from 0.1 to 2 kg/kg, respectively. In the first two columns of
Table 1 the operating conditions for the cyclone attrition tests with
used ‘‘u’’ and fresh ‘‘f’’ VPO catalyst are shown.
Included in the last columns of Table 1 are the steady-state
attrition rates rc  standard deviation s—measured for the various
operating conditions. These steady-state attrition rates rc are
calculated as a mean value of the attrition rates measured for each
pass through the cyclone under steady-state conditions. As it can be
seen in Fig. 6 under steady-state conditions the attrition rates still
scatter slightly. To assess the measurement error the standard
deviation of the attrition rates measured for each pass through the
cyclone is calculated
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N
uX
u ðx  xÞ2
u i
t i¼1
s¼ (8)
N1
N is the number of values, xi is a single sample – the attrition rate
measured for a single pass through the cyclone – and x is the mean
value of the samples – the steady-state attrition rate. For the
calculation of the standard deviation only the attrition rates under
steady-state conditions, respectively the attrition rates measured
after six passes through the cyclone are used.
In addition the mean value of the steady-state attrition rates for
multiple tests at the same operating conditions are given in Table
1. If the test was repeated more then two times the standard
deviation of the steady-state attrition rates measured in the
multiple tests was calculated according to Eq. (8).
Under steady-state conditions the mass of elutriated particles is
very small. Hence the measurement of the filter’s weight change is
the major error source in the attrition tests. In order to decrease the
sample taking error, the weight change of the filters was not
measured after each pass through the cyclone. This procedure was
only used in some experiments and after the material was already
passed five times through the cyclone. To assess the accuracy of the
measurement the relative error is calculated by the standard
deviation. The relative error is below 15% for most experiments.
The main criterion for the distinction between abrasion and
fragmentation is the characteristic change in the particle size
distribution. To analyze if pure abrasion or fragmentation is the
prevailing attrition mode, the particle size distributions of the used
and fresh VPO material before and after the experiments are
compared. The particle size distributions after attrition tests at two
 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65 61

Fig. 7. Mass particle size distribution of fresh VPO before and after attrition tests in
gas cyclone at two different operating conditions. Each attrition test comprised 15
passes through the cyclone.
Fig. 9. SEM image of fresh VPO after 15 passes through the cyclone at operating
conditions of uc = 20 m/s and mc = 1.0 kg/kg.
operating conditions – uc = 20 m/s, mc = 0.1 kg/kg and uc = 25 m/s,
mc = 0.5 kg/kg – together with the particle size distribution of the
material before it was used in the attrition tests are shown in Fig. 7
(fresh VPO) and Fig. 8 (used VPO).
In these experiments the materials were subjected to high
mechanical stress. It can be seen that the diameter of the mother
particles is just slightly reduced. Furthermore the stress during the
attrition tests does not lead to a significantly broader particle size
distribution or a smaller mean diameter. Hence the comparison of
the particle size distributions does not show evidence for
fragmentation of the used and fresh VPO particles.
In addition, samples of used and fresh VPO catalysts were
examined with the scanning electron microscope after they were
used in cyclone attrition tests. From the SEM images it follows, that
the used VPO particle samples show no significant change in shape
and surface structure. Sometimes broken particles are seen. The
comparison of the SEM images of fresh VPO material before and
after cyclone attrition tests shows that some particles are broken
after 15 passes. Moreover the edges of particles are chipped off and
the surface seems to be smoother (Fig. 9).
An image of the fine particles collected on the filters is shown in Fig. 10. SEM image of the filter catch at operating conditions of uc = 25 m/s and
Fig. 10. The particles are very fine with diameters well below 5 mm. mc = 0.5 kg/kg with used VPO material.
In Fig. 11 the measured steady-state cyclone attrition rates and
the attrition rates calculated using the steady-state cyclone
attrition model of Eq. (5) are shown as a function of the gas inlet
velocity.

Fig. 8. Mass particle size distribution of used VPO before and after attrition tests in
gas cyclone at two different operating conditions. Each attrition test comprised 15
passes through the cyclone.
Fig. 11. Measured and calculated steady-state cyclone attrition rates for varying gas
inlet velocities and constant solids loading mc = 0.5 kg/kg. The measured data points
are mean values if tests were repeated (Table 1). Error bars indicate the standard
deviation between the tests—only available for operating conditions with more
then two repeated tests. The model in Eq. (5) is calculated with Cc = 0.72  103 and
Cc = 3.91  103 [s2/m3] for used and fresh VPO, respectively.
62 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65

It can be seen, that the steady-state attrition rate of both

materials increases with the gas inlet velocity. The attrition rates
measured in experiments with the fresh VPO material are
significantly higher than the attrition rates measured for used
VPO material.
The relationship between the gas inlet velocity and the attrition
rate of used VPO in the cyclone attrition model is seen to be
confirmed for cyclone inlet velocities of 15 and 20 m/s (Fig. 11).
The attrition rates measured at a gas inlet velocity of 25 m/s
deviate from the rest. The model under-predicts the extent of
attrition. Especially for used VPO this deviation is significant. Even
if the measurement errors are taken into account this finding
cannot entirely be explained.
It is interesting to note, that Reppenhagen [15] observed the
same tendency. In attrition tests with FCC-catalyst at constant
solids loading of 0.3 kg/kg the deviation occurred for gas inlet
velocities exceeding 20 m/s. Reppenhagen explained the deviation Fig. 12. Measured and calculated steady-state cyclone attrition rates for varying
by the additional production of fine particles resulting from the solids loadings mc and constant gas inlet velocity uc = 20 m/s. The measured data
combination of abrasion and fragmentation. If the gas velocity points are mean values if tests were repeated (Table 1). The model in Eq. (5) is
respectively the mechanical stress exceeds a certain threshold, the calculated with Cc = 0.72  103 and Cc = 3.91  103 [s2/m3] for used and fresh
VPO, respectively.
attrition mechanism will change from pure abrasion to a
combination of abrasion and fragmentation [15].
According to Section 1 the attrition mechanism fragmentation 4.3. Attrition in the bubbling-fluidized bed
should be identifiable by characteristic changes in the particle size
distribution of the solid material in the underflow. However, the Bubble-induced attrition was investigated for superficial gas
comparison of the measured particle size distributions before and velocities u of 0.1, 0.2, 0.25 and 0.3 m/s with a constant bed mass of
after attrition experiments in the present case showed no evidence 450 g for each test.
for particle fragmentation. Furthermore the visible number of The cut size of the gravity separator varied from 16 mm at a
broken particles on the SEM images of samples before and after superficial gas velocity of 0.1 m/s to 28.5 mm at a superficial gas
attrition tests is not significantly different. The missing evidence of velocity of 0.3 m/s. The mean diameter of the bed material changes
particle fragmentation could possibly be explained by the special during the attrition experiments, because particles with diameter
structure of the VPO catalyst. The particles consist of an attrition- smaller then the separation diameter are elutriated. The mean
resistant shell and a less attrition-resistant catalytically active particle diameters calculated with the PSD’s of the bed material
porous core [16]. Once the attrition-resistant shell is damaged or after the test are dp = 49; 54; 55.5 and 59 mm for the superficial gas
removed, the porous core might be pulverized and elutriated. velocities u = 0.1, 0.2, 0.25 and 0.3 m/s, respectively.
Hence the combination of abrasion and fragmentation would The time dependent attrition rates, measured at operating
significantly increase the attrition rate, without leading to the conditions of u = 0.2 m/s and mb = 450 g are shown in Fig. 13.
characteristic changes in the particle size distribution resulting The attrition rates decrease with the time and reach a steady-
from fragmentation. state. The high attrition rates in the beginning of the attrition test
The influence of the solids loading mc on the steady-state result from a sifting of the bed material: Some particles present in
cyclone attrition rate rc was investigated at a constant gas inlet the bed material before the test are smaller than the cut size of the
velocity of 20m/s. The resulting mean steady-state attrition rates gravity separator and are elutriated together with attrition
for each process condition are shown in Table 1. produced fine particles. The parameter umin in Eq. (2) represents
According to the cyclone attrition model the steady-state the threshold gas velocity of the bubble-induced attrition and is in
attrition rate rc decreases with increasing solids loading. This result this work defined as umin = umf, because it is the bubble activity
can be explained by a ‘‘cushioning’’ effect [15]: When more which causes the attrition. It has to be considered, that the
particles are fed to the cyclone the chance for an individual particle
to contact the wall is decreased.
In Fig. 12 the measured steady-state attrition rates and the
attrition rates calculated with the cyclone attrition model (Eq. (5))
are shown as a function of the solids loading mc.
The cyclone attrition model is obviously able to describe the
relationship between the cyclone attrition rate rc and the solids
loading mc over a wide range for both materials. In the test with
used VPO a significant deviation occurs for the solids loading of
0.1 kg/kg. This deviation might be explained by the missing
cushioning effect, leading to higher mechanical stress and a change
in the attrition mechanism [15], as discussed above.
The parameter Cc in Eq. (5) was fitted to the steady-state attrition
rates measured for used and fresh VPO, respectively (Table 1). The
attrition rates measured for used VPO at the gas inlet velocity of
25 m/s and at the solids loading of 0.1 kg/kg were excluded for the
fitting, because they are deviating significantly from the rest. The
Fig. 13. Bubble-induced attrition rates plotted versus the elapsed time; measured in
parameters Cc are 0.72  103  20% and 3.91  103  14% for used fluidized bed attrition test unit (ID = 0.05 m) with porous plate gas distributor,
and fresh VPO, respectively. The relative error of these parameters is u = 0.2 m/s and mb 450 g (used VPO). The dashed line indicates the steady-state
related to the relative errors of the measurement. attrition rate.
 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65
Fig. 14. Measured bubble-induced steady-state attrition rates of used VPO catalyst
plotted versus the excess gas velocity (u  umf). The error bars represent the
standard deviation of the attrition rates measured during the attrition test under
steady-state conditions. The solid line is a linear fit of the steady-state attrition rates
measured at 0.2–0.3 m/s. According to Eq. (2) the slope of the fit is the attrition
constant Cb. The test at 0.1 m/s only comprised 50 h of operation and was therefore
excluded from the fitting.
definition of the parameter umin influences the attrition rate
constant Cb. Therefore the same definition of the threshold velocity
must be used for the data evaluation to give comparable results.
In Fig. 14 the measured steady-state bubble-induced attrition
rates versus the excess gas velocity (u  umf) are plotted. The error
bars represent the standard deviation of the attrition rates
measured during the attrition test under steady-state conditions.
The solid line represents a linear fit of the data points measured at
0.2–0.3 m/s. Following Eq. (2) (with umin = umf) the fitting must
include the origin and therefore the line should start with rb = 0 at
(u  umf) = 0. The slope of the fit is according to Eq. (2) the attrition
rate constant Cb = 3.31  108 [–]. The attrition test at a superficial
gas velocity of 0.1 m/s was excluded for the fitting, because of the
insufficient test duration of only 50 h.
In the attrition tests only small amounts of material have been
used, because the amount of test material available was limited.
Therefore the mass of elutriated particles per time is very small.
This leads to higher relative errors. Moreover keeping the
operating conditions constant during the long-term tests is
difficult and variations may lead to errors. The relative error of
the parameter Cb  40% is related to the standard deviation of the
measurement.
4.4. Attrition in fluidized bed with submerged gas jet
Two jet attrition tests with jet gas velocities of 100 and 50 m/s
were preformed. The jets issued in fluidized beds operated at
superficial gas velocities of 0.2 and 0.1 m/s, respectively.
The attrition rates measured in the attrition test with a jet gas
velocity uor = 50 m/s and a superficial gas velocity of 0.1 m/s are
plotted versus the elapsed time (Fig. 15).
As in the bubble-induced attrition tests, the attrition rate
decreases with the time. The steady-state attrition rate Rtot is
1,93  109 kg/s. This measured attrition rate is the sum of the
steady-state jet attrition and the steady-state bubble-induced
attrition:
Rtot ¼ Rj þ r b  mb (9)
The steady-state jet attrition rate Rj = 7.2  1010 kg/s is calculated
according to Eq. (9) by subtracting the product of the specific
bubble-induced attrition rate rb = 0.32  108 kg/(kg s) – calculat-
ed with the model in Eq. (2) – and the mass of bed material
mb = 0.38 kg from the measured total attrition rate Rtot. The
63
Fig. 15. Attrition rates measured in a fluidized bed with submerged gas jet
(uor = 50 m/s, u = 0.1 m/s) for used VPO plotted versus the elapsed time. The
diameter of the orifice was 2 mm and the bed material used was 380 g. The dashed
line represents the steady-state attrition rate.
material specific jet attrition rate constant Cj in the jet attrition
model in Eq. (3) is calculated as Cj = 2.5  105 s2/m3 with the gas
density rg = 1.184 kg/m3.
The total attrition rate under steady-state conditions Rtot
measured in the attrition test with uor = 100 and u = 0.2 m/s is
1.15  107 kg/s. The jet attrition rate constant Cj calculated with
the jet attrition model for these operating conditions is
Cj = 4.1  104 s2/m3. Comparing the attrition rate constants for
the two different operating conditions shows a distinct deviation.
This deviation might be explained by the change in attrition
mechanism. Resulting from the high mechanical stress induced by
the jet gas velocity of 100 m/s the attrition mechanism changes
from pure abrasion to a combination of abrasion and fragmenta-
tion. Therefore the jet attrition rate constant determined in the
attrition test with a jet gas velocity of 50 m/s is regarded as the jet
attrition rate constant under pure abrasion conditions. Since the
calculation is influenced by the bubble-induced attrition rate and
the calculation depends on one attrition test, the relative error of Cj
is  40%.
4.5. Ranking of the VPO attrition resistance
The attrition of VPO materials was investigated for different
attrition sources. In order to rank the attrition propensity of the
VPO materials, the specific attrition rate constants C are compared
with those obtained for other materials previously. These
constants are independent of the operating conditions and should
therefore allow the comparison of the attrition propensity of
different materials. Since the specific attrition rate constants
strongly depend on the attrition models used to evaluate the
measured test results, the given models in Eqs. (2), (3) and (5) for
bubble-induced attrition, jet attrition and attrition in gas cyclone,
respectively, were used for the calculation. In some of the previous
works other models have been used, therefore the specific attrition
rate constants had to be recalculated from the measured attrition
rates with the above-mentioned models.
In Table 2 the particle size-independent steady-state attrition
constants Cc, Cb and Cj for used and fresh VPO investigated in this
work are compared with other materials tested previously by the
author’s group.
Xi [17] investigated the attrition of different materials in
fluidized beds, in fluidized beds with submerged gas jets and
circulating fluidized beds. The FCC-catalyst (designated FCC 1993
in Table 2) used in the attrition test, was spent catalyst received
64 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65
Table 2
Particle size-independent steady-state attrition constants Cc, Cb and Cj.
Status of catalyst Designation of catalyst Cc
103 [s2/m3]
Used FCC 2005 1.9
FCC 85-A 1.55
FCC 97-A 0.56
FCC 93 – 1.37
‘‘u’’ VPO 0.72
Fresh FCC 97-G 1.20
FCC 97-R 0.60
FCC 97-A 2.87
FCC 94-K 2.24
HA-HPV – 1.12
VPO G a – –
VPO G b – –
‘‘f’’ VPO 3.91
from a company. Another material he used was the high alumina-
high pore volume (HA-HPV) catalyst from Akzo Chemie. Further-
more he investigated a non-industrial VPO material produced by
Uihlein in the work group of Prof. G. Emig [18]. The jet-induced
attrition tests of the latter VPO material was performed under an
atmosphere of either air (VPO G a in Table 2) or 1.8 vol.% n-butane
in air (VPO G b in Table 2) with a jet gas velocity uor = 100 m/s and a
bed temperature of 420 8C.
Reppenhagen [19] investigated the attrition behavior of five
different FCC-catalysts and a non-doped catalyst carrier 94-
K(fresh) in the gas cyclone, in the bubbling-fluidized bed and in
the bubbling-fluidized bed with submerged gas jets. The 85-
A(used) was obtained from a refinery in 1985 as equilibrium
catalyst. The 97-A(fresh) and 97-A(used) were a fresh and
equilibrium catalyst, respectively, obtained from a company more
recently. The 97-R(fresh) consist of almost spherical particles
whereas the 97-G(fresh) has a almost identical composition but
was irregularly shaped. The mean particle diameters of the
materials vary from 88 to 112 mm.
The mean particle size of the FCC-catalyst (designated as FCC
2005 in Table 2) Klett [20] used for attrition tests in bubbling-
fluidized bed and gas cyclone was 57 and for attrition tests in
fluidized bed with submerged gas jet 66 mm, respectively. The jet
gas velocity was 50 m/s with a superficial gas velocity in the
column of 0.5 m/s. The superficial gas velocity in the bubbling-
fluidized bed attrition tests was 0.4 m/s for FCC-catalyst. In the
cyclone attrition tests the gas inlet velocity uc was 18 m/s and the
solids loading mc was 0.3 kg/kg.
The comparison of the attrition constants Cc in Table 2 shows
that the used VPO material investigated here has a low attrition
propensity in gas cyclone under abrasion conditions. The attrition
constant is similar to those measured for industrial FCC-catalysts.
The latter materials are known to be attrition-resistant when used
in fluidized bed processes. The fresh VPO has a significantly higher
attrition rate constant, which is similar to the behavior of the other
catalysts and is probably due to the particle shape, production
method, presence of agglomerates etc.
The attrition rate constant Cb (Table 2) measured in the
bubbling-fluidized bed for used VPO seems to be slightly higher
than those measured for the other materials. However, the
deviation in attrition rate constants of the VPO catalyst and
previous materials is in the range of the experimental
errors. The reason of the slightly higher attrition rates is not
clear. It may be that the test duration was not long enough.
Furthermore only small amounts of bed material were used in
the underlying tests, since the total amount of VPO in this study
was limited. The relative error of the measurements is therefore
increased.
Cb Cj Author
108 [1/m] 105 [s2/m3]
0.45 2.9 Klett [20]
– 5.26 Reppenhagen [19]
– 2.19
4.24 Xi [17]
3.31 2.5 This work
1.9 – Reppenhagen [19]
– 2.63
– 7.67
– 3.29
3.91 Xi [17]
24.93
15.76
– – This work
The particle size-independent steady-state attrition rate con-
stants Cj measured for attrition in fluidized bed with submerged
gas jet for used VPO is comparable to those obtained for FCC-
catalysts.
5. Conclusion
The attrition propensity of used and fresh VPO catalysts
subjected to different typs of mechanical stress was investigat-
ed. The attrition rates of the materials were measured for
bubble-induced attrition, attrition induced by a gas jet issuing in
a fluidized bed and attrition in a gas cyclone. The attrition rates
measured are compared with attrition models adopted from
literature. A good agreement between the model and measure-
ment results for attrition in gas cyclone under pure abrasion was
observed. Attrition rates measured for operating conditions
resulting in high mechanical stress significantly deviate from the
rest. According to Reppenhangen’s studies [15] these deviations
may be explained by a change in the attrition mechanism from
pure abrasion to abrasion in combination with fragmentation.
The particle size-independent attrition rate constants of the
tested VPO materials are calculated for each attrition source
using the attrition models. These constants are compared to
those of other materials investigated in the authors group
previously. The attrition propensity of the used VPO material
under mechanical stress in gas cyclone and fluidized bed with
submerged gas jet is low, i.e. in the range of industrial FCC-
catalyst. The attrition propensity of used VPO in bubbling-
fluidized bed seems to be slightly higher than those measured
for FCC-catalyst. However, the deviation is in the range of the
experimental error. In agreement with previous findings for
other catalysts the cyclone attrition rate constant for fresh VPO
catalyst is higher than for used catalyst.
Acknowledgment
The authors acknowledge the support received from Mr. Volker
Röder conducting the attrition tests in his Studienarbeit.
References
[1] D. Merrick, J. Highley, AIChE Symp. 70 (1974) 367–378.
[2] W.G. Vaux, Am. Power Conf. 40 (1978) 793–802.
[3] R.M. Contractor, H.E. Bergna, U. Chowdhry, A.W. Sleight, in: J.R. Grace, M.A.
Shemilt, L.W. Bergougnou (Eds.), Fluidization VI, Engineering Foundation,
1989, 589–596.
[4] V.N. Blinichev, V.V. Streltsov, E.S. Lebedeva, Int. Chem. Eng. 84 (1968) 615–
618.
[5] M. Pell, in: J.C. Williams, T. Allen (Eds.), Handbook of Powder Technology, Vol. 8.
Gas Fluidization, Elsevier, 1990, pp. 97–106.
 A. Thon, J. Werther / Applied Catalysis A: General 376 (2010) 56–65
[6] J. Werther, in: M. Bohnet, G. Bellussi (Eds.), Ullmann’s Encyclopedia of Industrial
Chemistry 7th ed., Fluidized-Bed Reactors, Wiley, 2008.
[7] J. Werther, J. Reppenhagen, in: W.C. Yang (Ed.), Handbook of Fluidization and
Fluid–Particle Systems, Attrition, Marcel Dekker, 2003, pp. 201–238.
[8] W.G. Vaux, D.L. Keairns, in: J.R. Grace, J.M. Matsen (Eds.), Fluidization, Particle
Attrition in Fluid-Bed Processes, Plenum Press, 1980.
[9] F.A. Zenz, E.G. Kelleher, J. Powder Bulk Solids Technol 4 (1980) 13–20.
[10] Y.C Ray, T.S. Jiang, C.Y. Wen, Powder Technol. 49 (1987) 193–206.
[11] G. Donsi, Combust. Flame 41 (1981) 57–65.
[12] J.J. Pis, A.B. Fuertes, V. Artos, A. Suarez, F. Rubiera, Powder Technol. 66 (1991) 41–46.
65
[13] U. Arena, A. Cammarota, L. Massimilla, L. Siciliano, P. Basu, Combust. Sci. Technol.
73 (1990) 383–394.
[14] J. Werther, W. Xi, Powder Technol. 76 (1993) 39–46.
[15] J. Reppenhagen, J. Werther, Powder Technol. 113 (2000) 55–69.
[16] H.E. Bergna, US-Patent Nr. 4769477, 1987.
[17] W. Xi, PhD Thesis, Hamburg University of Technology, 1993.
[18] K. Uihlein, PhD Thesis, Universität Karlsruhe, 1993.
[19] J. Reppenhagen, PhD Thesis, Hamburg University of Technology, 1999.
[20] C. Klett, PhD Thesis, Hamburg University of Technology, 2005.