Chemical Engineering Journal 171 (2011) 841–869

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Chemical Engineering Journal

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Review

Fluidized bed synthesis of carbon nanotubes – A review

Kinshuk Dasgupta a,b , Jyeshtharaj B. Joshi b,c,∗ , Srikumar Banerjee c,d
a
Materials Group, Bhabha Atomic Research Centre, Mumbai 400085, India
b
Department of Chemical Engineering, Institute of Chemical Technology, Mumbai 400019, India
c
Homi Bhabha National Institute, Mumbai 400094, India
d
Department of Atomic Energy, Mumbai 400001, India

a r t i c l e i n f o a b s t r a c t

Article history: Carbon nanotube is one of the most talked about materials in recent years due to its unique proper-
Received 14 December 2010 ties and potential applications in different fields. Out of different techniques, catalytic chemical vapour
Received in revised form 21 April 2011 deposition in a fluidized bed is the most promising technique for bulk production of this exotic mate-
Accepted 10 May 2011
rial. The objectives of this review are to bring out the science and technology behind this process, the
present commercial scenario and to draw a future roadmap. We have critically examined the published
Keywords:
literature on the nanoparticle fluidization, different forces involved in it and the hydrodynamics of a
Carbon nanotube
nano-agglomerate fluidized bed. The importance of use of discrete elemental method and computational
Fluidization
Hydrodynamics
fluid dynamics simulation in the fluidization of carbon nanotubes has also been highlighted. Different
Mathematical modeling preparation routes of catalyst materials have been compiled. The reaction and growth mechanisms of
Catalysis nanotubes, including modeling have been discussed. The data on the effects of different process parame-
Nanostructure ters on the quality and quantity of nanotubes have been critically analyzed. It has been indicated that the
available data are scattered in nature and further understanding in the mechanism is required in order
to find out the rate controlling step(s) and scale-up of the process. The present commercial scenario of
carbon nanotube market has been depicted. At the end, based on the present knowledge gaps, future
roadmaps have been suggested.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction potential applications, like electrodes for electrochemical double

Carbon nanotube (CNT) is one of the most investigated mate-
rials since it was rediscovered by Ijima [1]. [Regarding debate on
discovery of carbon nanotubes see the article by Monthioux and
Kuznetsov [2]]. Its attractiveness comes from its unique physi-
cal, chemical, mechanical and thermal properties originating from
the small size, cylindrical structure, and high aspect ratio of
length to diameter. A single-walled carbon nanotube (SWCNT)
consists of a single graphene sheet wrapped around to form a
cylinder. A multi-walled carbon nanotube (MWCNT) is concentri-
cally nested cylinders of grapheme sheets. CNTs have extremely
high tensile strength (≈150 GPa, more than 100 times that of the
stainless steel), high modulus (≈1 TPa), large aspect ratio, low den-
sity (1100–1300 kg/m3 , one-sixth of that of stainless steel), good
chemical and environmental stability, high thermal conductivity
(∼3000 W/m/K, comparable to diamond) and high electrical con-
ductivity (comparable to copper). Carbon nanotubes have different
∗ Corresponding author at: Institute of Chemical Technology, Department of
Chemical Engineering, N. P. Marg, Matunga (E.), Mumbai 400019, India.
Tel.: +91 22 33612106/+91 22 25597625; fax: +91 22 33611020.
E-mail addresses: jb.joshi@ictmumbai.edu.in, jbjoshi@gmail.com (J.B. Joshi).
layer capacitors [3], field emitters [4], nano-electronic devices [5],
hydrogen storage [6], as functional polymers [7], etc. Researchers
have also reported making of conductive, electromagnetic and
microwave absorbing and high-strength composites, fibers, sen-
sors, inks, energy storage and energy conversion devices, radiation
sources and nanometer-sized semiconductor devices, probes, and
interconnect using carbon nanotubes [8–15]. Recently, strong
and stretchable CNT fibers were spun from 0.65-mm-long CNT
forests, which have the strength and Young’s modulus of 1.91 GPa
and 330 GPa, respectively [15]. SWCNT/PVA composite fibers are
tougher than any natural or synthetic organic fiber described so
far [9]. Obviously the bulk production of carbon nanotubes in an
economic way is the route for feasibility of these applications.
CNTs are generally synthesized by electric arc discharge method,
laser ablation method, catalytic chemical vapour deposition (CVD),
flame synthesis, solar energy route, etc. [16–20]. The common fea-
ture of arc discharge and laser ablation methods is the need for
high amount of energy, which is supplied by means of an arc dis-
charge or laser to induce the reorganization of carbon atoms into
CNTs. The temperature used is even higher than 3000 ◦ C, which is
beneficial for good crystallization of the CNTs, thus, the products
are always produced with good graphite alignment. However, the
basic requirements of these systems, including vacuum conditions

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.05.038
842 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Nomenclature
rC0 initial rate of carbon formation, s−1
a activity of catalyst, dimensionless 
rBi kinetic rate for species i in the bubble phase, mol/g/s
aS residual activity of catalyst, dimensionless 
rEi kinetic rate for species i in the emulsion phase,
A pre-exponent constant in CNT growth expression mol/g/s
Ama Hamaker constant (macroscopic theory), J R particle/agglomerate radius, m
AR column section area, m2 R vector running through mass centre to contact
b0 number of holes of the distributor per surface area point, m
of column, m−2 Ru universal gas constant, J mol−1 /K
cdo fluid drag coefficient on an isolated particle, dimen- R1 , R2 radii of the adhering agglomerates, m
sionless Ra CNT growth rate, s−1
Cb carbon concentration at the carbide–metal inter- Rca constant of perfect gases, cm3 Torr/mol/K
face, mol/m3 Rep particle Reynolds number, dimentionless
CB concentration of bubble phase, mol/m3 t unit vector along tangential direction
CE concentration of emulsion phase, mol/m3 t time, s
CS carbon surface concentration, mol/m3 T torque, Nm
CS0 carbon surface concentration at gas side, mol/m3 T temperature of synthesis
da aggregate diameter, m TK bed temperature, K
dp particle diameter, m u fluid phase velocity in computational cell, m/s
D reactor diameter, m U superficial gas velocity, m/s
DB bubble diameter, m U0 inlet superficial gas velocity, m/s
DB0 initial bubble diameter, m Uave average superficial gas velocity, m/s
e energy dissipation rate, m2 s−3 UB velocity of bubbles, m/s
E activation energy for CNT growth, J mol−1 UB∞ velocity of an isolated bubble, m/s
ff fluid drag force, N Uc transition velocity, m/s
ff0 fluid drag force on an isolated particle, N Umb minimum bubbling velocity, m/s
fc contact force, N Umf minimum fluidization velocity, m/s
fd viscous contact damping force, N Use serious entrainment velocity, m/s
F volumetric fluid–particle interaction force, N v velocity of a single particle, m/s
F cohesion force, N V volume of particles inside computational cell, m3
FG buoyant weight of a single aggregate, N VB volume of bubbles, m3
F0 inter-phase mass transfer coefficient, s−1 VC volume of cloud, m3
g acceleration due to gravity, m/s2 VE volume of emulsion, m3
hk height above the distributor of the kth compart- VS∞ terminal settling velocity, m/s
ment, m V volume of the computational cell, m3
hk height of the kth compartment, m wCNT weight of CNT, g
H hardness of the bodies in contact, N m−12 x order of reaction
I moment of inertia, kg/m2 Z0 distance where the van der Waals force is maxi-
k turbulent kinetic energy, m2 s−2 mum, m
k coordination number, dimensionless
kB coefficient of segregation-diffusion, s−1 Greek letters
kc number of particle in the computational cell, dimen- ˛ defined by equation (30)
sionless ˛B ratio of gas velocities as defined in the equation (40)
kd deactivation kinetic constant, s−1 ˇ defined by equation (30)
kG defined by equation (27) ε voidage in the bed (gas hold-up)
kr regeneration kinetic constant, s−1 εmf voidage in the bed at minimum fluidization velocity
K ratio of cohesion force to single-aggregate buoyant ı displacement or overlap between two contacting
weight, dimensionless particles, m
L height of the bed, m ıK Kronecker delta, dimensionless
m mass of the particle, kg  defined by equation (37)
mcata weight of catalyst in the bed, g  coefficient of friction, dimensionless
n unit vector along normal direction  fluid viscous stress tensor, kg/m/s
n exponent in Richardson–Zaki equation, dimension-  spring constant, N m−1
less f fluid viscosity, kg/m/s
Nc number of gaseous species in the system f bulk viscosity, kg/m/s
p fluid pressure in computational cell, Pa  viscous contact damping coefficient, kg/s
PX partial pressure of gas X, Pa h Lifshitz–van der Waals constant, J
P bed pressure drop, Pa
a aggregate density, kg/m3
qEB inter-phase transfer due to the increase of total
f fluid phase density in computational cell, kg/m3
number of moles, s−1
G gas density, kg/m3
r geometric mean of the radii of asperities in contact,  tensile stress, Pa
m  time, s
r1 , r2 radii of the adhering asperities, m
empirical coefficient, dimentionless
rC carbon formation rate, s−1 ω angular velocity, s−1
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
and continuous graphite target replacement, pose difficulties to the
large-scale production of CNTs. In contrast CVD has been proven
to be a preferred route for large-scale production of carbon nan-
otubes [21–25]. Here the carbon is deposited from a hydrocarbon
(or other carbon bearing source) in the presence of a catalyst at tem-
peratures lower than 1200 ◦ C. The CNT structure, such as its wall
number, diameter, length, and alignment, can be well controlled
during the CVD process. Thus, the CVD method has the advan-
tages of mild operation, low cost, and controllable process, and
is the most promising method for the mass production of CNTs.
Various scalable processes have been reported with CVD meth-
ods, including “Carbon Multiwall Nanotubes” of Hyperion Company
[26], “CoMoCATTM Process at SWeNT” of the University of Okla-
homa [27,28], “HiPCO Process” of Rice university [29–31], and
f U 2 (1 − ε)
“Nano Agglomerate Fluidized Bed” process of Tsinghua University
[32,33]. Though the fluidized bed technique is the most promising
route for the mass production of carbon nanotubes, fluidization of
nano-sized particles is itself a challenge. The published literature
contains four good reviews [34–37] on the present subject mat-
ter. These reviews have focused mainly on the morphology and
the growth mechanisms of CNTs. In addition to this, we need to
understand the present status of fluidized bed reactors with respect
to synthesis of CNT. It is known that the characteristic features of
conventional fluidized bed are different from that of nanoparticle
fluidization. In this review paper, we shall try to bring out how the
challenges regarding fluidized bed synthesis of CNTs have been met
so far. Our intention is to critically examine the published literature
on (1) hydrodynamics of the fluidized bed using nanoparticles, (2)
effect of different process parameters on the morphology and yield
of carbon nanotubes in a fluidized bed, (3) mechanism of synthe-
sis of CNTs by CVD method, (4) kinetics and estimation of overall
rate of reaction, (5) simulation and mathematical model of the CVD
f U 2 Rep
process in a fluidized bed and (6) design and scale-up procedure for
fluidized bed synthesis. An attempt will be made to bring out the
knowledge gaps and suggestions will be made for future work in
this area.
2. Fluidization of nano particles
The most critical part for the synthesis of carbon nanotubes
using a fluidized bed is to design and synthesize the supported
catalysts suitable for fluidization. Generally transition metals (e.g.
Fe, Co, Ni) and their compounds are used as the catalysts in CVD
process [21–24]. These catalysts are dispersed on the supported
materials, like, alumina, magnesia, silica, zeolite, etc., having nano-
sized pores (<50 nm). The nano-sized supported catalysts made by
such a way are very cohesive in nature. In this section we shall
discuss briefly the basics of fluidization and their applicability in
the case of nanoparticles. In a normal fluidized bed the force bal-
ance is carried out on a single particle. However, in the case of
nanoparticles, inter-particular attractive force plays an important
role. The nanoparticles form agglomerate and then fluidize. The
force balance in this case cannot be applied to a single nanoparti-
cle. Experimentally it is very difficult to find out the inter-particular
force. Computer simulations using discrete element method (DEM)
and computational fluid dynamics (CFD) are necessary to find out
the particle–particle and particle–fluid interactions. The following
sub-sections deal systematically the nanoparticle fluidization, its
hydrodynamics and DEM–CFD simulation.
2.1. Nanoparticles and Geldart’s classification
Geldart [38] classified the particles into four groups. Group A
particles (small mean size and having particle density <1400 kg/m3 )
exhibit a non-bubbling fluidization regime and the bed of the
843
particles undergoes relatively higher expansion upon fluidization;
Group B particles (having mean size between 40 ␮m and 500 ␮m
and density between 1400 kg/m3 and 4000 kg/m3 ) begin to bubble
immediately upon fluidization; Group C particles (mean size below
that of group A) are cohesive and extremely difficult to fluidize in
the strict sense; Group D particles (mean size >500 ␮m with high
density) can produce deep spouted beds. The supported catalysts
meant for synthesis of CNTs, fall into Group C. Therefore, it is a
technical challenge to make them fluidize.
The pressure drop in a fixed bed is given by Ergun equation
[39]. The Ergun equation describes the relationship between the
piezometric pressure drop, P, and fluid velocity, U:
2
P f U(1 − ε)
= 150 2
+ 1.75 (1A)
L dp ε3 dp ε3
At minimum fluidization velocity, the weight of the bed is
entirely supported by the flowing medium, and beyond this value
the pressure drop remains practically constant, however, the bed
expands. The Richardson and Zaki equation [40] is generally used to
describe the bed expansion behaviour at steady state as a function
of fluidization velocity:
U = VS∞ εn (1B)
where VS∞ is the terminal velocity and n is a parameter which is
a function of particle Reynolds number. The above two equations
are empirical in nature. Pandit and Joshi [41] developed a unified
equation based on force and energy balance. The following equation
developed by them can be used to predict the pressure drop in fixed,
expanded and fluidized beds.
P dp ε4.8 18
= + 0.33 (2)
L (1 − ε)
These equations are based on fluid drag, buoyancy and gravita-
tional forces acting on particles (for details refer to [42,43]). When
the particle size goes down to about 10 ␮m, the inter-particle forces
become of the same order of magnitude as those of gravity and drag
[44]. Further decrease in the particle size to values in the nano-
scale range results in an increase of attractive forces by almost two
orders of magnitude [44]. The strong inter-partcle forces have been
found responsible for the formation of agglomerates. Under these
conditions the hydrodynamics of the fluidized bed is reported to
be dependent on the shape and density of the agglomerate rather
than those of primary particles [44].
Experiments were reported [45,46], which show that addition
of small quantities of a non-volatile liquid to a material in Geldart’s
group B causes its fluidization behaviour to move through group
A to group C. Rhodes et al. [47] observed the similar phenomena
by using magnetic field in the fluidized bed. Due to these external
factors (i.e. liquid bridge and magnetic field) the inter-particular
cohesive force increases. Molerus [48], Sevelle and Clift [46] and
Rhodes et al. [47] suggested that the B/A and A/C boundaries in
the Geldart classification diagram for dry powders corresponded
to specific ratios of the inter-particle cohesive force to fluid drag
force. Due to the sixth power dependence on the distance between
the particles, the van der Waals attractive interactions are promi-
nent for nanoparticles. Inspite of cohesive nature of the particles,
several studies have shown that these particles can be fluidized
homogeneously even without the aid of any external assistance
[49,50]. According to Hakim et al. [51], the relative strength of
intra-aggregate inter-particle forces (forces within the aggregate
holding nanoparticles together) to inter-aggregate inter-particle
forces (forces between aggregates) plays an important role in deter-
mining the characteristics of nanoparticle fluidization. This relative
strength was inferred from the sphericity of the aggregates during
fluidization. For nanoparticles that are not zero-dimensional or that
844 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Fig. 1. Images of Aerosil R974 particles and their aggregates: (A) TEM image with magnification of 20,000; (B) TEM image with a magnification of 50,000; (C) SEM image of
particle aggregates; (D) SEM image of the surface of a particle aggregate [54].

can coalesce into fractal subsets, the inter-particle forces vary sig-
nificantly with the packing structure and can be exploited for the
fluidization of ultrafines. An aerogel Cu/Al2 O3 powder has shown
promise as another candidate for improving fluidization [52]. More
recently, a synthesized silicon aerosol has been fluidized smoothly
via self-agglomeration by Wang et al. [53].
sure drop was low and the motion of particles was negligible. The
pressure drop gradually increased with increasing gas velocity, and
a point was reached at which the pressure drop balanced the weight
of the particles per unit area. As the velocity was further increased,
the pressure drop continued to increase until the pressure drop was

2.2. Pressure drop and bed expansion characteristics

Wang et al. [54] studied the fluidization behaviour of Degussa

Aerosil R974 (silica) powder, using a fluidized bed made up of glass
having 50 mm i.d. and 900 mm height. They used a sintered bronze
porous distributor plate of 3 mm thickness and 10 ␮m pore size.
The primary particle size and density were 12 nm and 2200 kg/m3 ,
respectively, with a bulk density of 30 kg/m3 and external surface
area of 200 m2 /g. TEM imaging showed that the primary particles
were joined together in chain and tree-like structure (Fig. 1A and
B) [54]. Consequently, these particles exist in the form of aggre-
gates, mostly in the 1–100 ␮m size range (Fig. 1C), with loose and
fluffy surfaces (Fig. 1D). The minimum fluidization velocity for the
particles was found to be around 2.5 mm/s. A typical curve of bed
pressure drop as a function of increasing velocity is shown in Fig. 2. Fig. 2. Variation of bed pressure drop as a function of increasing superficial gas
When the gas velocity was very low, e.g., below 1 mm/s, the pres- velocity (even packing; static bed height = 25 mm) [54].
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 845

Fig. 3. Variation of bed pressure drop as a function of increasing superficial gas Fig. 4. Bed expansion as a function of superficial gas velocity [54].
velocity (uneven packing; static bed height = 17.5 mm) [54].

the velocity as a function of voidage obeys the Richardson–Zaki

about 15% above the weight of the particles per unit area. Further equation. This type of fluidization of nanoparticle agglomerates has
increase in gas velocity led to the start of fluidization and evident been termed as agglomerate particulate fluidization (APF) [55]. For
bed expansion. other nanoparticles, fluidization results in a relatively limited bed
The amount of pressure drop above the weight of the particles expansion and large bubbles rise up very quickly through the bed.
per unit area has been termed as “overpressure”. The overpressure This type of fluidization has been termed agglomerate bubbling
was required for overcoming the adhesion between the particles fluidization (ABF) [55]. Zhu et al. [50] studied gas fluidization char-
and the distributor plate, together with any friction between the acteristics of 11 different nanopartcle materials. These are listed
particles and the walls. The authors observed that the overpressure in Table 1. Typical fluidization curves, that is, bed expansion and
remained constant (about 1 Pa) when the static bed height was rela- pressure drop curves, for APF and ABF nanoparticles are shown
tively small (e.g., below 30 mm). At static bed heights above 50 mm, in Figs. 5 and 6, respectively. For both APF and ABF nanoparticle
an overpressure of up to 3 Pa was observed, indicating that the wall agglomerates, the pressure drop increases with an increase in the
friction plays an increasing role in the overall pressure drop for superficial gas velocity and then reaches a plateau and becomes
these conditions. The fluidization behaviour shown in Fig. 2 repre-
sents a ‘normal’ packed-bed condition where the particles are fairly
loosely packed and uniformly distributed. In this case, the overpres-
sure enables simultaneous breaking of the bonding between the
particles and the distributor plate, as well as any interconnected
channels and cracks formed for the lower velocity range. So, soon
after the occurrence of fluidization, the pressure drop decreases to,
and remains at, a level, which approximately balances the weight
of the particles per unit area.
In the case of initial uneven packing of particles in the bed, the
pressure overshoot was found to be accompanied by vigorous erup-
tion of particles via local channels. With an increase in the gas
velocity, the channels were observed to merge and the fluidiza-
tion was found to first occur near the central region of the bed. The
fluidized region then expanded towards the walls until the whole
bed became fluidized. The reason for delayed fluidization near the
walls was that the particles tended to stick around the corners of
the distributor plate. Since only a proportion of the particles partic-
ipated at the initial stage of fluidization, we would expect a region
where the pressure drop is smaller than the weight of the particles
per unit area. An example of this behaviour is shown in Fig. 3. A
typical example of bed expansion ratio as a function of superficial
gas velocity (U) is shown in Fig. 4. The bed was found to expand
even for U < Umf , where Umf is minimum fluidization velocity. This
behaviour is believed to be a distinct feature of nanoparticle flu-
idization. However, bed expansion was found to be not appreciable
for U < Umf . The bed expansion ratio increased almost linearly with
increasing gas velocity for U ≥ 2 × Umf . These results suggest that,
provided that full fluidization is achieved, nanoparticles possess
certain properties of Group A particles of Geldart classification. The
reason for nanoparticles to achieve homogeneous fluidization is
commonly believed to be aggregation of the primary nanoparticles
to form larger and loose aggregates.
For some nanoparticles, very smooth fluidization occurs with Fig. 5. Typical fluidization curves for APF nanoparticles (A) Degussa Aerosol® R974
continuous bed expansion, practically no bubbles are observed, and (B) Degussa Aerosol® R106 [50].
846 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Table 1
Fluidization behaviour of different nanoparticles [50].

Powder Wettability BET (m2 /g) Size (nm) Bulk density Material Material Fluidization type Surface modification Measured Umf
(kg/m3 ) density (kg/m3 ) (mm/s)

R974 Hydrophobic 170 12 33.24 SiO2 2560 APF DDS 2.3

R805 Hydrophobic 150 12 45.88 SiO2 2560 APF DDS 6.5
R104 Hydrophobic 150 12 62.90 SiO2 2560 APF OCS 4.3
R711 Hydrophobic 150 12 45.88 SiO2 2560 APF MCS 3.8
COK84 Hydrophobic 170 12 37.86 SiO2 –Al2 O3 :7–1 2740 APF None 12.6
R106 Hydrophobic 250 7 41.49 SiO2 2560 APF OCS 2.3
A 300 Hydrophilic 300 7 39.00 SiO2 2560 APF None 11.0
R972 Hydrophobic 110 16 39.00 SiO2 2560 APF DDS 2.9
OX50 Hydrophilic 50 40 121.33 SiO2 2560 ABF None 40.3
A 90 Hydrophilic 90 20 52.00 SiO2 2560 ABF None 77.1
TiO2 Hydrophilic 50 21 128.29 TiO2 4500 ABF None 51.7

DDS; dimethyl-dichlorosilane; OCS, octamethylcy-clotetrasiloxane; MCS, methacrylsilane.

independent of the gas velocity. For APF nanoparticles, the authors
observed that the bed fluidized and expanded very uniformly with-
out bubbles with a large expansion ratio of up to 500% or more,
the bed expansion increased with increasing gas velocity, and the
agglomerates distributed uniformly within the bed. As shown in
Fig. 6, for ABF nanoparticles, the bed expanded very little with
increasing gas velocity (<50%), and the authors observed large bub-
bles rising up very quickly through the bed; the agglomerates
distributed nonuniformly within the bed and the smaller agglomer-
ates appeared to be smoothly fluidized in the upper part of the bed,
whereas the larger agglomerates could be found moving slowly
at the bottom. Based on the experiments, the authors concluded
that the difference in fluidization behaviour between APF and ABF
depends largely on the bulk density and the primary particle size.
The fluidization of relatively small (<20 nm) nanoparticles with a
bulk density <100 kg/m3 (see Table 1) appear to behave as APF,
whereas larger and heavier nanoparticles are likely to behave as
ABF.
Joshi et al. [56] have discussed the stability criteria and
the transition from homogeneous (particulate) to heterogeneous
(aggregative or bubbling) behaviour in multiphase reactors. They
followed the following steps: (1) the starting point was the equa-
tions of continuity and motion for solid–fluid dispersion under
turbulent conditions; (2) the equations of motion of both the
phases were combined to eliminate the pressure term; (3) per-
turbations were introduced and the equations of continuity and
motion were written in terms of perturbation variables; (4) the
resulting equations were linearized; (5) the velocity perturbations
were eliminated using the equation of continuity and a final lin-
earized equation was obtained in terms of perturbation in fractional
hold-up; (6) under homogeneous regime, any perturbation to the
flat hold-up profile decays with respect to time. In contrast, if the
small perturbations grow with time, transition to heterogeneous
regime occurs. The authors presented the parametric sensitivity
of the criteria in the form of stability maps. The particle phase
dispersion coefficient has been shown to be the most important
parameter governing the stability.

2.3. Measurement of cohesive force

As nanoparticles normally appear in the form of particle aggre-

gates, it would be reasonable to consider the basic entity of
fluidization in a nanoparticle bed to be nanoparticle aggregates.
Taking an aggregate of diameter of 220 ␮m and an apparent density
of 22 kg/m3 , such aggregates (which should be viewed as pseudo-
particles) lie close to the A/C boundary in Geldart’s diagram. As per
Wang et al. [54] the characteristic behaviour of nanoparticle flu-
idization depends on the relative importance of the cohesion force
between particle aggregates.

2.3.1. Inter-aggregate cohesion force based on Lifshitz’s

macroscopic theory
A well-known approach for calculating the cohesion (attractive)
force between two spheres, F, is based on Lifshitz’s macroscopic
theory [57], as expressed in equation below:
 
h h
F= 2
R 1+ (3)
8Z0 82 Z03 H

where Z0 is a distance at which the van der Waals force is maxi-

mum (approximately 4 × 10−10 m). The term h is a Lifshitz–van
Fig. 6. Typical fluidization curves for ABF nanoparticles (A) Degussa Aerosol® OX50 der Waals constant, which is related to the Hamaker constant Ama
(B) Degussa titanium dioxide P25 [50]. by h = (4/3)Ama . The value of Ama is 8.55 × 10−20 J for SiO2 parti-
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 847

cles [58]. The value of H in the equation represents the hardness of

the bodies in contact, which is 108 N m−12 for undeformable solids.
Parameter R is a geometric mean of the radii of the spheres in con-
tact, defined as R = (R1 R2 )/(R1 + R2 ), where R1 and R2 are radii of the
spheres. The inter-aggregate force comes out to be 67.2 nN.

2.3.2. Inter-aggregate cohesion force based on measurement of

pressure overshoot
Valverde et al. [59] have shown that, provided that the static
bed height is small, the tensile yield stress of a cohesive powder
() approximately equals the pressure overshoot at incipient flu-
idization. The tensile stress is related to the cohesion force between
the aggregates by the following expression [60]:
(1 − ε)Fk
= (4)
da2 
where da is aggregate diameter, k is coordination number, i.e., the
number of contacts per aggregate, and ε is void fraction around the
aggregates. Jaraiz et al. [191] proposed the following cubic equa-
tion for calculating the coordination number from the void fraction
around the aggregates:

k = 17.517 − 41.838ε + 37.082ε2 − 10.815ε3 (5)

For a voidage around the aggregates of 0.47, the value of k is
found to be about 4.92. For da = 220 ␮m and  = 1 Pa from the exper-
iments by Wang et al. [54], then F = 58.3 nN.
2.3.3. Reconciling fluidization behaviours of nanoparticles to
macro-sized particles
For a particle aggregate to be fluidized, the drag force acting on
the aggregate should approximately balance its buoyant weight. It
is therefore instructive to compare the cohesion forces in relation
to the buoyant weight of a single aggregate (FG ). The value of FG can
be calculated from the following expression [54]:
1 cated that a non-uniformity in the radial solid distribution with a
FG =
6da3 (
a −
G )g
where
a and
G are aggregate and gas density, respectively. Let on the microstructure scale, the gas–CNT flow was more homoge-
us use K to denote the ratio of the inter-aggregate cohesion force
to the buoyant weight of a single aggregate, i.e., K = F/FG . The value
of K provides a good indication of the characteristics of fluidization
[47]. As a rough guide, the value of K should be below 3 for Group B
particles, between about 3 and 40 for Group A particles, and above
40 for cohesive particles [47].
Fig. 7. Dependence of bed expansion and pressure drop on gas velocity in a CNT
nano-agglomerate fluidized bed [61].
lower than that of Geldart-A particles, due to the weak interaction
among the CNT agglomerates and their highly porous structure.
This indicated that good fluidization behaviour could be achieved
only with strong turbulence of the fluidized bed, because of strong
interaction between agglomerated CNT. The particulate fluidiza-
tion was not always uniform, and it depended on the gas velocity.
In aggregative fluidization, the distribution of the time-averaged
solid fractions also showed a stronger radial non-uniformity than
Geldart-A particles. An analysis of the transient density signals indi-
(6) lot of aggregation among agglomerates near the wall with increas-
ing volume fraction of the dense phase near the wall. However,
neous than Geldart-A particle fluidization, which was good for gas
mixing, and led to high gas dispersion coefficients of about 10 m2 /s
in the axial direction and 102 m2 /s in the radial direction.
2.5. Discrete element method (DEM) and computational fluid
dynamics (CFD) simulation

2.4. CNT hydrodynamics in a nano-agglomerate fluidized bed
CNT hydrodynamics in a nano-agglomerate fluidized bed has
been studied by Yu et al. [61]. A fluidized bed of plexiglass of
280 mm i.d. and 2 m high was constructed to investigate for this
purpose. The CNT materials were synthesized by propylene decom-
position on a Fe/Mo/Al2 O3 catalyst in a fluidized bed. The prepared
CNTs had a low packing density of 50 kg/m3 with agglomerate
sizes ranging from several to 500 ␮m. The authors measured the
axial profiles of section-averaged solid fractions from pressure drop
profiles. They also used electrical conductance method to mea-
sure the local solid concentrations. A steady state hydrogen tracer
technique was used to obtain the axial and radial gas dispersion
coefficients. The dependences of bed expansion and pressure drop
on gas velocity in a CNT nano-agglomerate fluidized bed is shown
in Fig. 7. A smooth and highly expanded fluidization was achieved,
but a strong hysteresis existed in the CNT fluidization curve. On
the defluidization branch, similar to Geldart-A particles, particu-
late fluidization, agglomerate bubbling fluidization, turbulent, and
fast fluidizations could be successively observed and distinguished
as shown in Table 2. However, Uc and Use of the CNTs were relatively
The gas–solid flow in a fluidized bed can be modeled at three
different length and time scales: (1) the processing equipment, (2)
the computational cell, and (3) the individual particles. Many corre-
lations have been proposed in the published literature to describe
the various performance characteristics of a fluidized bed at the
processing equipment level (for instance, Ergun equation [39] for
the estimation of the minimum fluidization velocity as a typi-
cal example). On the other hand, the modeling of the gas–solid
flow at the computational cell level has been developed mainly
on the basis of the local average technique [62], where both gas
and solid phases are treated as interpenetrating continuum media
while local mean variables instead of the point variables are used
in the Navier–Stokes equation, which is then solved by the com-
putational fluid dynamics (CFD). This continuum approach can
provide useful information about the gas–solid flow and has actu-
ally dominated the modeling of fluidization processes for years, as
summarized by Gidaspow [63]. However, in addition to the dif-
ficulty of providing constitutive correlations for the inter-phase
transfer of mass, momentum and energy within its continuum
framework, this approach is unable to model the discrete flow
characteristics of individual particles. On the other hand, the tech-
848 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Table 2
Fluidization characteristics of CNT agglomerate [61].

Umf (m/s) Umb (m/s) Uc (m/s) VS∞ (m/s) Use (m/s) dp (␮m)
a (kg/m3 )

Observed 0.017 0.038 ∼0.1 0.205 >0.2 416 61.1

nique called discrete element method (DEM) established by Cundall Based on the above assumption, Newton’s second law of motion
and Strack [64], when applied to granular systems, in which the is used to describe the motion of individual particles. Thus, at any
motion of individual particles is obtained directly by solving New- time , the equation governing the translational motion of particle
ton’s second law of motion, has emerged to be an important tool i is
in powder/particle technology research [65]. The direct incorpora-
tion of CFD into DEM to study the gas fluidization process so far dvi  ki

mi = ff,i + (fc,ij + fd,ij ) + mi g (7)

has been attempted by Tsuji et al. [66] and by Hoomans et al. [67].
In their modeling, the gas flow is determined by the conventional
continuum approach, giving information for calculating the fluid
drag force acting on individual particles. The motion of individ-
ual particles is then obtained by solving Newton’s second law of
motion. This gives information for determining the porosity from
the coordinates of individual particles for the further evaluation of
gas flow field. These authors have shown that this approach is very
promising in simulating the gas fluidization process at the indi-
vidual particle level. However, in addition to their oversimplified
assumption of inviscid fluid for the gas-phase flow, a major draw-
back of the model proposed by Tsuji et al. [66] is that only very soft
particle ( = 800 N m−1 ) can be used due to the difficulty of keep-
ing the numerical solution stable. This introduces an unrealistically
large displacement or overlap between the contacting particles and
hence results in erroneous fluid drag and inter-particle forces. To
avoid large overlaps, Hoomans et al. [67] proposed a hard sphere
model, in which the particle motion is computed based on the
kinematics of hard sphere collision and the stiffness of a particle
is therefore effectively chosen to be infinite. However, one major
drawback of the hard sphere approach is that detailed informa-
d
j=1
where mi and vi are, respectively, the mass and velocity of particle
i, and ki is the number of particles in contact with this particle. The
forces involved are: the fluid drag force (ff,i ), gravitational force
(mi g), and inter-particle forces between particles i and j which
include the contact force (fc,ij ), and viscous contact damping force
(fd,ij ). Because the true density of particle is usually much larger
than that of gas, the buoyancy force acting on particle i, has been
ignored in Eq. (7).
The gravitational and fluid drag forces act on the mass centre
of particle i, while the inter-particle forces act at the contact point
between particles i and j. The inter-particle forces will generate a
torque, (Tij ), causing particle i to rotate. For a spherical particle of
radius Ri , Tij is given by Tij = Ri x·fc,ij , where Ri is a vector running
from the mass centre of the particle to the contact point (its mag-
nitude equals to Ri ). Thus, the equation governing the rotational
motion of particle i is:
dωi  ki
Ii = Tij (8)
d
tion about inter-particle forces is greatly suppressed [68], which, j=1
like the model of Tsuji et al., makes comprehensive understand-
where ωi is the angular velocity, and Ii is the moment of inertia of
ing of the complex force related fluidization phenomena difficult.
particle i.
Furthermore, the coupling of DEM and CFD equations, which are
To solve Eqs. (7) and (8), the forces involved need to be deter-
actually developed on the basis of different length and time scales,
mined a priori. To demonstrate the principles of evaluating these
has not been fully recognized as an important issue and correctly
forces, a collision between two particles i and j, as shown in Fig. 8,
achieved in the above two models. This may prohibit the general
will be discussed. Here we define that two particles are in contact
application of this combined DEM–CFD approach. Let’s now discuss
if the distance between their mass centres is less than the sum of
the basics of DEM and CFD and the combined approach.
their radii. The inter-particle forces involved in Eq. (7) are deter-
mined from their normal and tangential components, represented,
2.5.1. Discrete element method
respectively, by fcn,ij and fdn,ij , and fct,ij and fdt,ij for particle i.
A particle in a fluidized bed can have two types of motion: trans-
lational and rotational, which are describe by Newton’s second law
2.5.1.1. Inter-particle forces. A number of models have been pro-
of motion. During its movement, the particle may collide with its
posed for the evaluation of the inter-particle forces, which can
neighbour particles or wall at the contact points and interact with
probably be grouped into three categories: the linear model, the
the surrounding fluid, through which the momentum and energy
non-linear model, and the non-linear hysteretic model. Their main
are exchanged. Strictly speaking, this movement is affected not only
features and applications in the DEM simulation have been studied
by the forces and torques originated from its immediate neigh-
by Johnson [69], Thornton and Yin [70] and Walton [71], among oth-
bour particles and vicinal fluid but also the particles and fluids far
ers. Generally speaking, a more sophisticated model can produce
away through the propagation of disturbance waves. The complex-
better results [72–74]. However, the linear contact force model is
ity of such a process has defied any attempts to model this problem
still widely used mainly due to its simplicity as well as reasonable
analytically.
accuracy [64,68,72,75]. Accordingly, the linear normal and tangen-
Even for the numerical approach, proper assumptions have to be
tial contact force models are used in the present study, so that
made in order that this problem can be solved effectively without
an excess requirement for computer memory or expensive iterative fcn,ij = −(n,i ın,ij )ni (9)
procedure. Similar to the concept proposed by Cundall and Strack
[64], it is assumed here that this problem can be solved by choosing and
a numerical time step less than a critical value so that during a
fct,ij = −(t,i ıt,ij )ti (10)
single time step the disturbance cannot propagate from the particle
and fluid farther than its immediate neighbour particles and vicinal where n,i , ın,ij and t,i , ıt,ij are, respectively, the spring constant
fluid. Then, at all times, the resultant forces on any particle can and displacement between particles i and j in normal and tangential
be determined exclusively from its interaction with the contacting directions, ni and ti are, respectively, the unit vectors along the nor-
particles and vicinal fluid. mal and tangential directions for particle i (Fig. 9). If |fct,ij | >  ij |fcn,ij |,
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 849

Fig. 8. Schematic of the forces acting on the particles i and j.

then sliding occurs, and the magnitude of the tangential force is

given by the Coulomb friction law, preserving the sign obtained
from Eq. (10), we get:
|fct,ij | = −ij |fcn,ij | (11)
where  ij represents the coefficient of friction between particles i
and j. The normal and tangential displacements in Eqs. (9) and (10)
are determined from the motion history of particles i and j. That is,
their calculation is related to the collision dynamics of two particles
as will be discussed in Section 2.5.1.3.
A system will eventually tend to be stationary as a result of the
inelastic collisions between particles if no external energy is added
to it. This mechanism can be simulated by introducing a viscous
contact damping force to consume the system energy during the
particle collisions [64]. The viscous contact damping forces for par- Fig. 9. Relative positions between particles i and j before collision: (A) separated;
ticle i along the normal and tangential directions are, respectively, (B) contacted.
given by
fdn,ij = −n,i (vr · ni )ni (12)
and drag force acting on a single particle, which is applicable to both
fixed and fluidized beds over the full practical range of particle
fdt,ij = −t,i [(vr · ti )ti + (ωi × Ri − ωj × Rj )] (13) Reynolds number. As per them the following equation holds:
where n,i and t,i are, respectively, the normal and tangential vis-
−
cous contact damping coefficients of particle i, and vr , is the velocity ff,i = ff 0,i εi (14)
vector of particle i relative to j, defined as vr = vi − vj . If sliding
occurs, then only friction damping is considered and viscous con-
where εi is the porosity around particle i, taken as the porosity in a
tact damping is vanished [64].
computational cell in which particle i is located. Here we define that
a particle is located in a cell as long as its mass centre is in this cell.
2.5.1.2. Fluid drag force. As implied in Eq. (7), the fluid–particle
The fluid drag force on particle i in the absence of other particles,
interaction force, i.e., the fluid drag force, should be determined
ff0,i and the empirical coefficient, , are, respectively, given by:
on the individual particle basis. This force is not only dependent on
the relative velocity of fluid and particle but also the presence of  
other surrounding particles [41,42,76–79]. It is extremely difficult ff 0,i = 0.5cd0,i
f Ri2 ui − vi  (ui − vi ) (15)
to determine this force theoretically. On the other hand, correla-
tions have been well established for the evaluation of this force at and
either processing equipment or computational cell level [39,40,80].
This force should be linked to the force at the individual particle  
(1.5 − log10 Rep )2
level in some way. With this realization, Joshi [42], Di Felice [81] = 3.7 − 0.65 exp − (16)
2
and Pandit and Joshi [41] proposed procedures to calculate the fluid
850 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

where ui is the fluid velocity in the computational cell, and cd0,i , is

the fluid drag coefficient, can be expressed as
 2
4.8
cd0,i = 0.63 + (17)
Re0.5
p,i

and Rep,i is the particle Reynolds number defined as

 
2
f Ri ui − vi 
Rep,i = (18)
f

where
f and f are the fluid density and viscosity, respectively.

2.5.1.3. Collision dynamics. The potential danger of false solutions

from the time integration procedures with non-linear dynamics has
been emphasized by Stewart [82]. In the past years, considerable
efforts have been made to develop a numerical scheme by which the
energy is identically conserved in the non-linear dynamics [83–86].
However, it appears that little attention has been given to the colli-
sion dynamics. Unlike the situations encountered in other transient
non-linear dynamic systems, the fast moving particles in a gas flu-
idized bed exhibit extremely complicated collision patterns: not
only the collision points but also the collision partners change dur-
Fig. 10. Schematic of the particles in a computational cell (shaded area).
ing the time evolution. In this case, the possibility for a particle to
collide with its partner via a free fly path is high, which, if not con-
sidered properly, will introduce a fictitious elastic energy stored in viscous stress tensor in Eq. (20) is given by an expression analogous
the colliding particles. This problem can be effectively solved by to that for a Newtonian fluid [62]. That is:
means of a collision dynamic model.  
 = (f − 23 f )∇ · u ıK + f (∇ u) + (∇ u)−1 (21)
2.5.2. Computational fluid dynamics where ıK is the Kronecker delta, and f is the fluid bulk viscosity.
In a gas fluidized bed, the presence of particles provides imper- As the fluid drag force acting on each particle is known (see
meable boundaries which force gas to detour its path and flow Section 2.5.1.2), according to Newton’s third law of motion, the
through the interstitial gaps or voids among particles. Meanwhile volumetric fluid–particle interaction force can be determined by
the gas flow produces a fluid drag force which, together with the
inter-particle forces, results in the motion of individual particles. 
kc

This motion in turn affects the gas flow. It is through this mutual ff,i
interaction that the continuum gas and discrete particles exchange i=1
F= (22)
their momentum and energy. This interaction greatly complicates V
the gas flow patterns in a fluidized bed so that the point variables of where V is the volume of a computational cell, and kc is the num-
gas-phase vary rapidly in both space and time. It is difficult even for ber of particles located in this cell.
a modern supercomputer to directly calculate these instantaneous By definition, the porosity in a computational cell is the ratio of
point variables of gas-phase with moving discrete boundaries when the void volume to the volume of the cell. As particles move around
the number of particles considered is large [77,87]. An alternative inside a fluidized bed, it is quite normal that a particle may have
way to solve this problem is the local average technique established parts of its volume located in adjacent cells as shown in Fig. 10.
by Anderson and Jackson [62], in which these rapidly varying point Taking this into account, if Vi is the volume of particle i inside a
variables are replaced by the local mean variables over a region computational cell, then the porosity in this cell is
which contains many particles but still small compared with the
macroscopic variations from point to point in the system. This tech- 
kc

nique has been widely used in the continuum approach of modeling Vi

fluidization process [63]. i=1
ε= (23)
According to this local average technique, the mass conservation V
and Navier–Stokes equations are expressed in terms of the local
CFD modeling of pressure drop and drag coefficient has been
mean variables over the computational cell. Thus,
carried out by Reddy and Joshi [77] in fixed and expanded beds
∂ε where Reynolds numbers were varied from 0.1 to 10000. They have
+ ∇ · (εu) = 0 (19) used k–e model, where k is the turbulent kinetic energy and e is the
∂
energy dissipation rate (for details see [77]). The values were in well
and agreement with the experimental results.
∂(
f εu) The application of CFD in the synthesis of CNT by CVD method
+ ∇ · (
f εuu) = −ε∇ p − F + ∇ · (ε ) +
f εg (20) has been employed by Kuwana and Saito Group [195–197]. While
∂
producing CNTs from xylene over Fe nanoparticles, derived from
where p, F and  are, respectively, the fluid pressure, volumetric decomposition of ferrocene, they considered two gas-phase reac-
fluid–particle interaction force and viscous stress tensor. tions and four surface reactions as given below [195]:
For the sake of solving the fluid-phase momentum equation, Gas-phase:
the constitutive correlations for the volumetric fluid–particle inter-
action force and viscous stress tensor are required. Here the fluid C8 H10 + H2 → C7 H8 + CH4 r 1 = k1 C X C H 0.5 (R1)
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
C7 H8 + H2 → C6 H6 + CH4 r 2 = k2 C T C H 0.5
Surface:
C8 H10 → 8C (nanotube) + 5H2 r 3 = kBTX C X
C7 H8 → 7C (nanotube) + 4H2 r 4 = kBTX C T
C6 H6 → 6C (nanotube) + 3H2 r 5 = kBTX C B
CH4 → C (nanotube) + 2H2 r 6 = kBTX C M
Where subscripts B, T, X, M and H denote benzene, toluene,
xylene, methane and hydrogen respectively. The rate constants
of the surface reactions were determined using the inverse CFD
technique based on measured tail gas concentrations. The fluid
dynamics model adopted by them, were based on 3-D, laminar
and steady state flow with both gas-phase and surface chemical
reactions. The conservation equations of mass, momentum, energy
and species were solved with the aid of the ideal gas law. The pre-
dicted production rate agreed well with the experimental data.
The authors also modeled nanoparticles formation from ferrocene
[196]. The simple two-equation model includes the nucleation, sur-
face growth and collision of nanoparticles. The dynamic equation
for monodisperse particle was combined with an asymmetric CFD
simulation. The model predicts that the diameter of the particle
increases with an increase in the reaction temperature and with
the radial distance from the centre of the reactor. During the CVD
process, the authors observed catalyst deactivation [197]. They cor-
related this effect with the apparent rate constant with a simple
exponential expression [197]. Applying the CFD model, they pre-
dicted the local yielding rate of nanotubes along the axis of the
reactor. The total yield was then computed by integrating the local
yielding rate over the growth surfaces.
Recently Kim et al. [198] demonstrated that the structural for-
mation of vertically aligned carbon nanotube (CNT) forests was
primarily affected by the geometry-related gas flow, leading to the
change of growth directions during the chemical vapour deposition
(CVD) process. By varying the growing time, flow rate, and direction
of the carrier gas, they investigated the structures and the formation
mechanisms of the vertically aligned CNT forests. The growth direc-
tions of CNTs were found to be highly dependent on the non-linear
local gas flows induced by microchannels. The angle of growth sig-
nificantly changed with an increase in the gas flows perpendicular
to the microchannel, while the parallel gas flow showed almost no
effect. A CFD model was employed to explain the flow-dependent
growth of CNT forests, revealing that the variation of the local
pressure induced by microchannels was an important parameter
determining the directionality of the CNT growth.
2.5.3. Coupling between CFD and DEM
Obviously, the modeling of the solid flow by DEM is at the
individual particle level, while the gas flow by CFD is at the com-
putational cell level. Through local averaging, the equations based
on the point fluid variables are transferred into continuum equa-
tions in terms of the local mean variables at the computational cell
level. The most obvious difference between the point and contin-
uum equations is the introduction of the volumetric fluid–particle
interaction force as an explicit term in Eq. (20); this inter-phase
force influences the point equations of motion only through their
boundary values at the discrete particle surface. Theoretically, it
is this term that reflects the coupling between DEM and CFD. It is
understood that the correct coupling must be made on the basis of
Newton’s third law of motion. That is, the fluid drag force acting
on the individual particles from the fluid phase will react on the
fluid phase from the individual particles. This principle is clearly
expressed in Eq. (22).
However, this important issue is not fully recognized in the
previous work [66,67]. These authors considered the fluid drag
851
(R2) force acting on a single-particle and fluid–particle interaction force
exerted on the fluid in a computational cell separately. As a result,
the sum of the fluid drag force acting on the discrete particles in
(R3) a computational cell will not necessarily equal the fluid–particle
interaction force on the same cell, i.e. Newton’s third law of motion
(R4)
is not satisfied. Theoretically their model is not correct.
(R5) In the work by Xu and Yu [88], the combination of DEM and CFD
is numerically achieved as follows. At each time step, DEM gives
(R6)
information, such as the positions and velocities of individual par-
ticles, for the evaluation of porosity and volumetric fluid–particle
interaction force in a computational cell by Eq. (22). CFD then uses
these data to determine the gas flow field which, by Eq. (14), yields
the fluid drag forces acting on individual particles. Incorporation
of the resulting forces into DEM produces information about the
motion of individual particles for the next time step. This procedure
clearly indicates that the description of the continuum gas and dis-
crete particle flows in a fluidized bed should be obtained only when
DEM and CFD are properly combined. The CFD–DEM approach has
been used by various researchers [89] for other applications also.
Now we are in a position to appreciate the necessity of DEM–CFD
simulation and verification by experiments for CNT fluidized bed.
Having understood this, in the next section we shall discuss how
the supported catalysts are made in order to use them in a fluidized
bed.
3. Preparation of supported catalysts
The supported catalysts for fluidized bed synthesis of carbon
nanotubes can be prepared by several techniques, like sol–gel,
co-precipitation, impregnation, or metalorganic chemical vapour
deposition (MOCVD).
In the heterogeneous sol–gel method, a porous precursor of the
active component is impregnated with the precursor of a textural
promoter taken in the estimated amount to have a given weight
ratio between active component and textural promoter in the end
product. The role of the textural promoter is to stabilize the active
component structure and to prevent its sintering in the course of
post treatments [90]. One generally uses hard-to-reduce oxides
(HRO) such as silica or alumina as textural promoters [91]. To
get iron/silica nanocomposite particles, one can mix, for instance,
tetraethoxysilane (precursor of textural promoter) with iron nitrate
(precursor of the active component) aqueous solution and ethanol.
The mixture is then gelated, dried to remove the excess water and
solvent and finally calcinated [92].
In co-precipitation method, precursor nitrates of a catalyst and
of a metal oxide support, e.g. Ni(NO3 )2 ·6H2 O and Mg(NO3 )2 ·6H2 O,
are mixed with an organic compounds like urea or citric acid and
water [93–95]. Heating the mixture leads to reduction of the pre-
cursors to form intimately mixed oxide particles.
The impregnation method consists of first dissolving a catalyst
precursor (e.g. iron oxalate) and then contacting a support with this
solution [96,97]. In this method, the whole precursor deposits onto
or into (in case of a porous material) the substrate. The solvent is
then evaporated and the catalyst dried [98]. In a case of organic
supports and molecules, except added incubation period [99], the
method essentially remains the same. Sometimes, a solution of
a catalyst precursor (e.g. cobalt-acetate or cobalt-nitrate) is also
brought in contact with a zeolite support [96,100]. But in this case,
the anion of the precursor is exchanged with an anion of the zeolite,
giving a new precursor molecule. Calcination allows the thermal
decomposition of the catalyst precursor and gives the catalyst
element in an oxidized form. In the ion adsorption–precipitation
method, the support is put in a catalyst precursor solution (e.g.
Co(H3 C–CO2 )2 ·4H2 O) [101]. An acid–base reaction takes place at
the surface of the support, leading to precipitation of the catalyst
852 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
precursor (cobalt-acetate in the example above). The reaction can
be controlled by the pH of the initial catalyst precursor solution.
The sample is then calcinated to get only the catalyst element in an
oxidized form.
In metalorganic chemical vapour deposition (MOCVD), a met-
alorganic precursor (e.g. iron pentacarbonyl) is vaporized and
carried to the reactor zone by a carrier gas [98]. Heating of the reac-
tor zone allows the precursor to decompose and to depose onto the
substrate.
4. Reaction and growth mechanism for carbon nanotubes
In the fluidized bed reactor the substrate (e.g. alumina, silica,
magnesia, carbon black etc. containing catalyst like Fe, Ni, Co or
mixture) on which the carbon nanotubes grow, needs to be flu-
idized using a carrier gas (like nitrogen, argon etc.) initially till the
temperature of synthesis is reached. Then the fluidization occurs
by the mixture of carrier gas and process gas (hydrocarbons like
methane, acetylene, propylene etc.) till the experiment continues.
The following steps are involved in the fluidized bed:
A. The hydrocarbon travels from the bubble phase to the emulsion
phase.
B. Mass transfer of hydrocarbon from emulsion to the external sur-
face of the substrate.
C. Diffusion of hydrocarbon from the pore mouth on the surface to
the surface of the catalyst.
D. Adsorption of the hydrocarbon onto the catalyst surface.
E. Reaction on the catalyst surface to produce carbon molecules.
F. Surface diffusion of carbon molecules in the catalyst.
G. Nucleation of CNT.
H. Growth of CNT.
I. Desorption of hydrogen and other gaseous products.
J. Diffusion of the gaseous products from the catalyst surface to
the substrate external surface.
K. Mass transfer from the substrate to the emulsion phase.
In the literature it is very difficult to find the rate of reactions for
the individual steps mentioned above related to CNT growth. There
is no clear mention about the rate controlling step in a fluidized bed
synthesis of CNT. Helveg et al. [155] suggested that surface diffu-
sion of the carbon molecules (step F) is the rate controlling step
whereas some researchers suggested that growth of CNT (H) is the
rate controlling step [115]. Morancais et al. [118] found the diffu-
sion of hydrocarbon through pore (step C) is the limiting step. In our
opinion in a fluidized bed depending on operational condition rate
controlling step can vary. As most of the reported data suggest that
the activation energy for CNT formation is greater than 35 kJ mol−1 ,
steps A, B, C, J and K should not be considered as rate controlling
steps. We have developed rate equations for the steps D, E, F, G, H
and I. The rate controlling step(s) can be found out by fitting the
curves corresponding to the above equations in the experimen-
tal data. These equations will be communicated later along with
analysis of the experimental data generated by us in this labora-
tory. In brief, the rate of deposition of CNT varies linearly with the
partial pressure of the hydrocarbon if step D is rate controlling. It
shows second order dependency with the ratio of partial pressure
of hydrocarbon to that of hydrogen if E or F is rate controlling and
third order dependency if H is rate controlling. We tried to apply
our analysis technique on the data given by Philippe et al. [157]. The
CNT deposition rate as given in their paper has been plotted against
the ratio of partial pressure of ethylene and hydrogen (Fig. 11). The
third order dependency on the ratio of the partial pressure suggests
that the rate controlling step is the growth of CNT (step H) as per
Fig. 11. Dependence of CNT deposition rate on the ratio of partial pressure of ethy-
lene to that of hydrogen as per data provided by Philippe et al. [157] and analyzed
by us.
our analysis. Following are some reported reaction mechanisms in
the published literature.
4.1. Kinetic models
The reports related to kinetics of carbon nanotube growth and
related mathematical models are very few in the literature. One of
the early stage reports by Cabero et al. [141] discusses the growth
kinetics of CNT by catalytic decomposition of acetylene, over an
iron supported catalyst. The mechanism of carbon filament for-
mation assumes that the carbon atoms, formed on the metallic
surface from the hydrocarbon decomposition, react to form sur-
face metallic carbide. The process of decomposition–segregation of
this carbide allows the carbon atoms to penetrate into the metallic
particle, and finally regenerate the metallic surface. The evolution
of the carbon concentration at the interface of the metallic carbide
and the metal particle, Cb , can be expressed according to first-order
kinetics,
dCb
= kB (CS − Cb ) (24)
dt
where the parameter kB represents the coefficient of
segregation–diffusion of the surface metallic carbide. It depends
on the diffusivity of the carbon through the surface carbide, the
carbide phase thickness, and the exposed surface area of this
carbide. CS represents the carbon surface concentration gener-
ated from the fed hydrocarbon decomposition (see Fig. 12). This
parameter is mainly affected by the gas composition, pressure, and
temperature during reaction. It also varies proportionally to the
remnant surface activity of the metal particles in the catalyst,
CS = CS0 a (25)
where CS0 is the carbon concentration at the gas side of the metal-
lic particles when the catalyst is not deactivated. This model also
considers that the catalyst can be deactivated by the formation of
encapsulating carbon. This carbon can be partially removed from
the catalyst surface by gasification with the hydrogen present in
the reaction atmosphere.
Consequently, the rate of catalyst deactivation is expressed as
da
− = kd a − kr (1 − a) = kG (a − aS ) (26)
dt
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 853

Fig. 12. Scheme with some parameters involved in the reaction kinetics of the
growth mechanism of CNTs [141].

where kd and kr are the deactivation and regeneration kinetic con-

stants, respectively. For a given catalyst, both kinetic parameters
are a function of the operating conditions, namely temperature and
gas composition. The catalyst residual activity, aS , and the parame-
ter kG , depend on kd and kr , and the relationships are expressed as
follows: Fig. 13. Influence of reaction temperature on the kinetic parameters: (A) evolution
kr of kd and kr at low temperatures, (B) evolution of rC0 and kB at high temperatures
aS = , kG = kd + kr (27) [141].
(kd + kr )
The authors then deduced the expressions for the carbon con-
centration in the interface carbide–metal particle, Cb , as is the reaction temperature, and x is the apparent reaction order
with respect to C2 H2 partial pressure. The growth temperature
Cb (t) = CS0 [aS + kG ˛ exp(−kG t) − kB ˇ exp(−kB t)] (28) dependence of the global growth rate is shown in Fig. 16A. An
and the carbon formation rate rC as Arrhenius-type plot of ln Ra vs. 1/T can give an estimate of apparent
activation energy of carbon deposition, E. It appears that according
rC (t) = rC0 [aS + kG ˛ exp(−kG t) − kB ˇ exp(−kB t)] (29) to Fig. 16A, the activation energy is a constant over the tempera-
ture range employed. Different slopes of Arrhenius plots indicate
The terms ˛ and ˇ are given by
that the activation energy of Ni-CNTs (104.6 kJ mol−1 ) is higher than
˛ = kB (1 − aS )/kG (kB − kG ) that of Co-CNTs (61.6 kJ mol−1 ). The CNT growth rate dependence
(30)
ˇ = (kB − kG aS )/kB (kB − kG ) on partial pressure of acetylene is illustrated in Fig. 16B. Since the
growth rate increases linearly with C2 H2 concentration, the global
Fig. 13 depicts the influence of reaction temperatures on
rate expression belongs to the first-order reaction.
the determined kinetic parameters. The proposed kinetic model
explains perfectly well the experimental observations: at low tem-
peratures the catalyst suffers deactivation, although initially the
carbon deposition rate has a high value, and at higher temperatures,
the catalyst does not suffer deactivation, and initially the carbon
deposition rate has a low value.
In Figs. 14 and 15, the influence of hydrogen and acetylene par-
tial pressure on equation kinetic parameters is presented. In Fig. 14
we can observe that the PH2 does not seem to affect the value of
parameter kB ; however, the value of rC0 reaches a maximum at PH2
of 7%. In Fig. 15, approximately first-order dependence between rC0
and kd with PC2 H2 is seen.
Hsieh et al. [156] synthesized carbon nanotubes over Ni and Co-
supported CaCO3 by decomposition of acetylene in a fluidized bed.
They expressed the CNT growth rate as
1 dwCNT

E

Ra = = A exp − (PC2 H2 )x (31)
mcata dt Ru T
where Ra is the global growth rate per unit mass of metal cat-
alyst, wCNT is the weight gained after CVD, mcata is the mass of
catalyst, A is the per-exponential constant, E is the apparent activa- Fig. 14. Influence of PH2 on the kinetic parameters (no deactivation of the catalyst)
tion energy of carbon deposition, Ru is the universal gas constant, T [141].
854 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Philippe et al. [157] recently carried out a kinetic study on

MWCNT synthesis by fluidized bed CVD technique using ethylene
as carbon source and Fe/Al2 O3 as catalysts. The Umf for the catalyst
powder was 35 mm/s at 650 ◦ C. The initial fluidization ratio U/Umf
was fixed at 4. The authors considered three apparent catalytic
reactions:

C2 H4 → 2CCNT + 2H2 (R7)

C2 H4 + H2 → C2 H6 (R8)

C2 H4 + 2H2 → 2CH4 (R9)

They deduced the kinetic equations for the above three reac-
tions as a function of Fe concentration (%Fe), mass of supported
catalyst (mcata ), bed temperature (T in Kelvin) and partial pressure
of ethylene (PC2 H4 ). The formation rates of CNT (R7), ethane (R8)
and methane (R9) are given by
Fig. 15. Influence of PC2 H2 on the kinetic parameters (partial deactivation of the
dR7

−29, 000   0.75
catalyst) [141].
= 69.97(%Fe · mcata )0.28 exp PC2 H4 (32)
dt RT
Between 550 ◦ C and 650 ◦ C
dR8

−17, 200  
= 15.95 exp PC2 H4 (33)
dt RT
Between 651 ◦ C and 750 ◦ C
dR8

94, 000  
= 6.44 × 10−6 exp PC2 H4 (34)
dt RT
dR9

−17, 000   1.37
= 1.76 exp PC2 H4 (35)
dt RT
The authors then implemented these kinetic laws in a bubbling
bed model [158] as discussed in the next section.

4.2. Mathematical model for fluidized bed synthesis of carbon

nanotubes

This model is based on modified Kato and Wen model [159,160].

The main assumptions of the original Kato and Wen model are as
follows:

(1) the fluidized bed is isothermal;

(2) it is represented by a series of compartments whose height is
equal to the mean diameter of bubbles at the corresponding
level;
(3) bubbles are growing by coalescence as they ascend through the
bed; the bubble diameter is given by the empirical relation of
Kobayashi [159]:

DBk = DB0 + k hk (36)

with
Uk
k = 1.4
p dp (37)
Umf

and
 0.4
6 U0 − Umf
DB0 = g−0.2 (38)
 b0

Each bubble is surrounded by a cloud of particles; its volume

was calculated by the relation of Davidson and Harrison [161]
3
VC = VB (39)
˛B − 1
with
Fig. 16. (A) Arrhenius plots for CNTs grown from different catalysts. (B) The CNT UB∞
growth rate at 850 ◦ C as a function of C2 H2 partial pressure [156]. ˛B = (40)
Umf /εmf
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 855

observed by GC during MWCNT synthesis. The gas flow increase

was due to the stoichiometry and to the relative contribution of the
three reactions involved. An increase of the gas flow rate created an
additional inter-phase transfer, leading to an increase of the bub-
bles volume without modification of their number. The evolution
of the superficial gas velocity along the height of the bed was calcu-
lated using an overall balance equation, which was solved in each
compartment of the bed. Moreover, all the parameters depending
on gas velocity were recalculated in each compartment. Following
are the modified mass balances equations.
For the bubble phase:

(AR UCBi )k−1 − (AR UCBi )k − [F0 VB (CBi − CEi )]k + [(1 − εmf )
P VC rBi ]

+ (qEB VB CEi )k = 0 (46)

For the emulsion phase:


[(1 − εmf )
P VE rEi ] + [F0 VB (CBi − CEi )]k − (qEB VB CEi )k = 0 (47)

The parameter qEB quantifies the gaseous flux transferred from

the emulsion to the bubble phase, per unit volume of bubble, due to
the variation of the gas flow rate induced by the chemical reactions.
It is equal to:
 
1 Rca TK 
NC

(qEB )k =
p rEi VE (1 − εmf )
VBk P
i=1 k
N 
C

− rBi VC (1 − εmf ) (48)
i=1 k

Fig. 17. Representation of a fluidized bed as per Kato and Wen [159]. The resolution of an additional overall mass balance allows
obtaining the evolution of the superficial gas velocity U from a
and compartment to another:
 Rca TK
UB∞ = 0.711 gDB (41) AR (Uk − Uk−1 ) =
p
P
(4) each compartment is constituted of two phases, (a) the bubble   N 
phase corresponding to the bubbles and their cloud, and (b) the

NC
C
 
× rEi VE (1 − εmf ) − rBi VC (1 − εmf ) (49)
emulsion phase, in which wakes are included; the volume of
i=1 k i=1 k
the bubbles for the kth compartment is given by:
Uk − Umf For each time step and for each compartment, the model solves
VBk = hk AR (42)
UBk simultaneously 2NC algebraic non-linear equations (mass balances
in the bubble and emulsion phases for each of the NC species), to
where
access to the concentration of each gaseous species in the two
UBk = Uk − Umf + UB∞k (43) phases at the exit of the compartment. The numerical method
of resolution was that of Newton–Raphson. The superficial gas
The resulting volume of the emulsion for the kth compart- velocity at the exit of the compartment was then calculated by
ment is given by: application of the overall mass balance Eq. (49) and recalculated if
VEk = AR hk − (VB + VC )k (44) necessary by an iterative procedure. This protocol was repeated for
each compartment until the sum of their height be equal to that of
(5) each phase is supposed to be perfectly mixed; the expanded height calculated at the beginning of each time step
(6) the convective mass transfer in the emulsion phase is with the Richardson and Zaki correlation [40]. The authors [158]
neglected; verified the validity of this correlation for the catalyst/MWCNT
(7) in each compartment, mass transfer occurs between the two composite powders at various contents in MWCNTs. An average
phases and the exchange coefficient is given by the Kobayashi superficial velocity in the bed Uave was then calculated and com-
correlation. pared with the value previously used for the estimation of the void
fraction ε. An iterative procedure was applied until an agreement
11
F0 = (45) was found between two consecutive calculations for Uave and ε.
DB
The deviation between the simulated and the experimental val-
The representation of the fluidized bed by the Kato and Wen ues in the bubbling regime was 17.3%. The authors also studied the
model is illustrated in Fig. 17. influence of reactor diameter and weight of catalyst for scale-up.
Following the work of Caussat et al. [160], the authors modified The simulation suggested that the productivity of 8 kg/h in a 45 cm
the mass balance equations of the model to consider the influence diameter reactor was possible in a semibatch condition.
of variations of gas flow rate induced by chemical reactions. Indeed, The mathematical modeling of the fluidized bed synthesis of
experimentally a non-negligible increase of the total flow rate was carbon nanotubes need to be consolidated in a separate article
856 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
Fig. 18. Schematic diagram of the root-growth and tip-growth mechanism [171].
taking into account the hydrodynamics, reaction mechanism and
CFD–DEM simulations, on which we have developed clarity. Some
work is also in progress in this laboratory.
4.3. Growth mechanism of CNT
The growth mechanism of CNTs has still not been fully under-
stood although different mechanisms have been proposed by
different researchers. It is also not clear whether the growth
mechanism is same for arc/laser synthesized CNTs as that of CVD
synthesized CNTs as the operating temperatures are much lower
for the latter case. There is an excellent review by Harris [162] on
the growth mechanism of CNTs by arc discharge and laser ablation.
There are theories and models on vapour phase growth [163,164],
liquid phase growth [165] and solid phase growth [166]. We are not
going into details of the mechanisms related to arc discharge/laser
ablation. Here we are interested in the growth mechanism of CVD
grown CNTs. The most accepted hypothesis for CVD grown CNTs is
similar to the diffusion precipitation mechanism proposed by Baker
and co-workers describing the growth of carbon fibers [140,167]. In
this model, the catalytic decomposition of a hydrocarbon feedstock
is initiated on the active transition metal surface and decomposes
into carbon atoms and hydrogen. This is followed by diffusion of
carbon into the metal particles until the solution becomes satu-
rated; supersaturation of the solution then results in precipitation
of solid carbon from the metal surface. Snoeck et al. [168] proposed
that the global driving force for carbon filament formation is the
difference in chemical potential between gas-phase and the carbon
filament. A carbon concentration gradient is thus created and it acts
as the driving force for diffusion process. A recent thermodynamic
study by Harutyunyan et al. [169] gives an insight how the decom-
position of the hydrocarbons affects the growth process of carbon
nanotubes. They found that although the decomposition reaction
of methane is endothermic an exothermic process is superimposed
which accompanies the nanotube growth making the net enthalpy
exothermic. On the other hand the precipitation of carbon from
the catalyst is an endothermic reaction. The temperature gradient
arising due to this is the driving force for the nanotube growth.
During the growth, the catalyst particle may be located at the tip
of a CNT (tip-growth) or at the base (base/root-growth) [170,171],
depending upon whether bulk diffusion or surface diffusion is dom-
inant (Fig. 18). This is also dependent on the interaction strength
between the catalyst and substrate.
The general consensus is that CNTs grow via the base growth
mechanism for strongly interacting metal catalyst and substrate
pairs, e.g., Fe and Al2 O3 , where the bonding energy between them is
high. However, other factors, such as the reaction atmosphere, also
play a role in determining the growth mechanism of CNT. Further
details are given in the papers of Alvarez et al. [172], Gavillet et al.
[173]. Recently, Philippe et al. [154] has proposed a growth mode
of MWCNTs on alumina supported iron catalyst. As per them, first,
MWCNTs are produced on the whole surface of the catalyst from
a cementite surface film. The regular consumption of the catalytic
film results in high CNTs density, which grow vertically aligned
to the surface of the catalyst grains. Between 30 min and 60 min
of reaction, entangled MWCNT growth appeared from secondary
catalytic sites, constituted by small nanoparticles located in the
porosity of the support and in strong interaction with this latter.
This second growth is accompanied by the fragmentation of the
catalyst grains. Earlier Yu et al. [174] have discussed the branching
mechanism of carbon nanotubes, which is depicted and explained
in Fig. 19.
The growth mechanism of MWCNT in a nano-agglomerate flu-
idized bed has been nicely discussed by Wei et al. [175]. The
multi-agglomerate structure that is formed is due to the CNT
growth on the powder catalyst. The SEM and TEM images of such
agglomerates are presented in Fig. 20. A model related to this
growth mechanism is depicted in Fig. 21. In the initial period, grow-
ing CNTs with a base growth mode crush the catalyst particles,
disrupt the structure, and form separated catalytic sites. Due to
the release of the stress inside the catalysts in this period, disor-
der in the graphite layer and defects occur during the initial carbon
deposition, as shown in the tips in Fig. 21B. With increased carbon
deposition, the catalysts get crushed as much as they can be and
the CNTs grow around the catalyst sites. The growing CNTs push
away and separate the sites from each other, leading to increas-
ing agglomerate size and decreasing density, until fragmentation
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 857

Fig. 19. Growth mechanism of the branching CNTs in FB-FCCVD. Drops of the ferrocene solution (A) can be evaporated to form small metal clusters (B), which aggregate (C)
and catalyze the growth of CNTs of 10 nm diameter (D). They can also be adhered on a CNT (E), forming a local active surface (F) and catalyzing the new generation of CNTs
(G) by the correlated growth mechanism. When the branching nanotubes close the end, the growth of branches deactivates (H) [174].

by ablation dominates the growing process (Fig. 21C and D). It is
noted that CNTs can be grown in a fluidized bed, where the solid
catalyst with CNTs are present as a low density material. This reac-
tor provides enough space for CNT agglomerate growth. However,
some fast growing CNT can penetrate another CNT agglomerate,
which causes the CNT agglomerate to ripen and grow fast. Then the
material is difficult to fluidize, which is harmful to the operation of
fluidized bed. Thus, a well-designed catalyst is the dominant factor
for this period. If the catalyst structure is too strong to destroy it
by the growing CNTs, the formation of sub-agglomerates is diffi-
cult, the inside of the catalyst can’t be used for the reaction, and the
carbon yield is much lower. On the other hand, too loose a catalyst
structure is easily broken into pieces and the sub-agglomerates get
formed. These, then, have a difficulty in forming stable agglomer-
ates, and, as a result remain in too small size and get entrained out
of the reactor.
Recently, Kunadian et al. [176] have proposed a model for
growth of MWCNT synthesized by a continuously fed CVD method.
Fig. 22 depicts the sequence of growth from ferrocene-xylene solu-
tion continuously pumped at 700 ◦ C on a quartz substrate. The
model has been proposed based on SEM and TEM observations.
The deposition of catalyst particles takes place first. This is fol-
lowed by the nucleation of carbon nanotubes via diffusion of carbon
atoms into the catalyst particles. With a lot of empty surface area
on the substrate, the catalyst particles are generously deposited
on the substrate and establish a strong interaction with the quartz
substrate, favoring nanotube growth via root-growth mechanism.
Initially, the nanotubes are sparsely distributed and grow in ran-
dom directions on the substrate. While the nanotubes continue
to grow in the axial direction, the tube walls close to the catalyst
particles begin to coarsen via epitaxial growth leading to the forma-
tion of taper-shaped nanotubes. The continuously supplied feed gas
produces more clusters of Fe atoms. The crowding of the nanotubes
prevents these newly formed catalyst particles from reaching the
substrate. These catalyst particles get deposited randomly on the
growing mat and grow via tip-growth due to weaker interaction
with the mat. The larger catalyst particles split and the growing
nanotube carries a portion of the catalyst on the tip end. A portion
of the catalyst splits further and gives rise to additional branches. As
the nanotube number density increases, they begin to align them-
selves into regular arrays in the vertical direction perpendicular to
the substrate carrying the coiled nanotubes on the growing end of
the mat.
In our opinion, in a fluidized bed CVD, the morphology and
growth rate of the CNT depend on the gas flow rate, hydrocarbon
concentration, temperature, size and shape of the initial agglom-
erate and catalyst loading and size. The gas flow rate affects the
mass transfer coefficient, the size and shape of the agglomerate
influences the internal diffusion of gas within pore, the temper-
ature, hydrocarbon concentration and catalyst loading determine
the reaction rate. The morphology of CNTs depends on the type and
size of catalyst and the carbon supply rate.
858 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
Fig. 20. A SEM image of agglomerate structure of MWCNTs [175]. 20B:TEM images
of CNT agglomerates from a Fe/Mo/Al2 O3 catalyst. The catalyst has been crushed by
CNT growth and a multi-stage CNT agglomerate was formed [175].
5. Effect of different parameters on synthesis of CNT
Table 3 summarizes the different parameters reported in the
literature used for the synthesis of carbon nanotubes in fluidized
beds.
5.1. Effect of catalysts
The size and the crystallographic orientation of the cata-
lyst nanoparticles play key role determining the morphology of
the carbon nanotubes. Many research groups observed a direct
dependence of the size of the catalyst and the diameter of the
CNT [22,96,99,102–106]. When the nanoparticles are deposited in
pores, the diameters of CNTs have a diameter roughly equal to
the diameter of the pore. Nikolaev [31] showed that the particle
size after CNT growth is larger than the CNT diameter, suggest-
ing that particles continue to grow even after nucleating a tube.
The relevant size of the nanoparticles for the resulting diameter
of the CNTs is thus their size at the time of nucleation. Forma-
tion of non-selective forms of carbon was observed by Cabero et al.
[107] with the iron–silica catalysts with higher iron content. They
explained this result by the fact that the degree to which metallic
iron aggregates upon reduction into metallic particles depends on
the iron content. Thus catalysts with higher iron content exhibit
larger metallic iron particles, leading to other forms of carbon than
nanotubes. Large particles therefore appear to be unable to catalyze
CNT growth. For a particle size smaller than 5 nm, the number of
atoms in low-coordinated positions is greater than 10% of the total
[108]. This may change the electron density of the nanoparticle
material or stabilize unusual faces or sites on the surface of the
aggregates [109]. Both will change the surface electronic structure,
what can in turn affect the catalysis process. On the other hand,
Hafner et al. [110] supposed that supply-limited growth allows
more time to anneal to the lowest-energy structure so that smaller
particles produce CNTs while larger particles are encapsulated. It is
believed that the supply rates of carbon atoms together with diame-
ter of the catalyst nanoparticles determine the diameter of the CNT.
SWCNT is grown when the catalyst particle diameter is less than
5 nm and carbon supply rate is low. Table 4 depicts the variation of
CNT diameter with catalyst diameter as reported in the literature.
Beyond the size of the catalyst nanoparticles, the crystallo-
graphic orientation of the supported nanoparticles also influences
CNT growth. Audier et al. [111] studied the crystallographic char-
acteristics of the catalyst particles at the end of carbon filaments
(tip-growth). Their study yields a correlation between the particle
orientation and the tube axis. More recently, Ermakova et al. [90]
claimed that hydrocarbon decomposition on nickel occurs on dif-
ferent edges of the nanoparticle due to anisotropy of nickel and
that the filament axis is found to be parallel to the nickel (1 1 1)
planes. The theoretical work of Shibuta and Maruyama [112] indi-
cates strong interaction between the hexagonal carbon network
formed in the first stage of the growth process and the structure
of catalytic metal atoms. The crystal orientation may thus play a
critical role in the determination of chirality. Similarly, Vinciguerra
et al. [113] showed that the (1,1,0) plane of iron (bcc) and the (1,1,1)
planes of cobalt and nickel (fcc) have the appropriate symmetry and
distances to overlap with the lattice of graphene sheet.
Govindaraj et al. [114] investigated the influence of catalyst
loading on carbon yield using Fe, Co and Ni catalysts (Fig. 23). With
increase in catalyst loading the carbon yield also increased. The cat-
alytic activity is maximum for Fe and minimum for Ni. The carbon
solubility and the carbon diffusion coefficient vary in Fe, Ni and Co,
which in turn affect the growth rate of CNT. The details regarding
this are given by Lamouroux et al. [115].
From the above discussion we understand that the size, crys-
tallographic orientation and the chemistry of the catalyst particles
influence the deposition rate and morphology of CNT.
5.2. Effect of reactor geometry
Table 3 shows that a wide range of reactors, having differ-
ent diameters and materials of construction, have been used by
the researchers for synthesizing carbon nanotubes by fluidized
bed technique. Use of fluidized bed was first reported by Her-
nadi et al. [116], where a 6.4 mm diameter quartz tube reactor
had been used. They observed significant soot formation along
with breakage of MWCNTs. They concluded that severe agitation
in the fluidized bed caused the damage to the CNTs and ruled
out using fluidized bed as a viable option for producing CNTs. In
fact, the selection of small bed diameter (6.4 mm) was not suit-
able for proper fluidization due to severe wall effect. This was
proved by Wang et al. [32] by producing MWCNT with 70–80%
purity at the rate of 5 kg/h using a fluidized bed of 250 mm diame-
ter. Today Bayer Materials Science (http://www.baytubes.com, Dec.
2009) and CNano Technology (http://www.cnanotechnology.com,
Dec. 2009) are producing MWCNTs commercially with the capac-
ity of 200 tons/yr and 500 tons/yr, respectively, using fluidized bed
technique. The materials of construction for the reactors are either
Table 3
Different parameters reported in literature for synthesis of carbon nanotubes.
Reactor dia. Height Distributor Catalyst Conc Substrate Preparation Substrate Charge Fluidizing Hydrocarbon Ratio Total flow Umf Temperature Time CNT type CNT dia Yield Purity (%) Reference
(mm) (mm) (%) method size (␮m) (g) gas rate (lpm) (m/s) (◦ C) (min) (nm)
Quartz 250 1000 Porous Fe NA Al2 O3 Co-precipitation NA 250 N2 /H2 C2 H4 0.5:0.5:10 180 0.006 500–700 30–60 MWCNT 10 5 kg/h 70–80% [32]
plate C3 H6
SS 40 1000 NA Fe NA Al2 O3 Co-precipitation 50 10 N2 C2 H4 2:3 .75 NA 550 300 MWCNT 3–16 30–150 g NA [178]
SS 196 1500 NA Fe-Mo NA Al2 O3 Co-precipitation 110 NA N2 C3 H6 NA NA 0.006 650 50 MWCNT ∼20 [117]
28 Fe NA Al2 O3 ≤5 N2 C2 H2 0.1 800 5 MWCNT 5–30 [179]
Fe 50–150
Fe 50–150
Ni 50–150
Co 50–150
50–150
22 Ni 60 Silica gel 50 Ar CH4 1:1 1 760 20 SWCNT 0.89–1.35 [19]
SS 53 1000 Fe 2.5 Al2 O3 Impregnation 100 100 H2 /N2 C2 H4 25:50:25 1 0.0014 650 10–120 MWCNT 17 0.22 g/m NA [180]
Quartz 28 NA Porous Fe 2 Silica Impregnation 100 10 H2 C2 H4 7:1 .14 0.0012 550–1050 30 MWCNT 9–15 [98]
plate
Quartz 6.4 NA Porous Fe 2.5 Silica Impregnation 15–40 0.03 N2 C2 H2 8:30 .038 NA 700 30 MWCNT NA NA NA [116]

K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

plate
40 Co-Mo 20 Al2 O3 NA NA Ar CH4 1:1 .833 NA 800 300 MWCNT 10–30 NA NA [181]
Ni-Cu
22 Fe 2.5–29 Silica 40–150 6 N2 /H2 C2 H2 580:15:10 0.605 NA 700 60 MWCNT 8–25 [107]
Quartz 30 Quartz Fe 1.5–15 MgO Impregnation 1.5 Ar C2 H2 368:42 0.41 450–850 20 SW/MW [182]
filter
Co La2 O3 0.1 N2 C2 H2 9:1 0.7 700 30 MWCNT 10–40 0.73 g/m [183]
SS 50 1000 SS grid Fe 2.5 Al2 O3 Impregnation 110 50 N2 /H2 C2 H4 685:1200:405 2.29 NA 650–750 5–150 MWCNT 15–17 [118]
50 ␮m hole
SS 53 1000 SS grid Fe 10.15 Al2 O3 MOCVD 322 60 N2 /H2 C2 H4 1:1:2 5.33 0.035 650 120 MWCNT 9.5–18.5 NA >90% [154]
50 ␮m hole
Inconel 601 1000 NA Fe-Co 2.5–5 Al2 O3 Impregnation 90–106 80 N2 /H2 C2 H4 8:2:1 3–6 Umf 0.012 600–800 20–60 MWCNT 15–30 NA NA [119]
52
SS 30 800 NA Fe, Ni, Co 1.5–5 Al2 O3 Impregnation 110 50–200 N2 /H2 C2 H4 8:2:1 3–5 Umf 0.012 550–800 15–90 MWCNT 15–30 3–29% [184]
SS 50 1000 0.05 mm Fe-Mo NA MgO NA 45–150 5 N2 /H2 C2 H2 /CH4 / 1:4:1 0.5–3 NA 600–1000 120 MWCNT Variable NA NA [152]
with bubble C2 H4 /C2 H6
cap
SS 40 800 SS mesh Ni, Co 5 CaCO3 Impregnation 100 NA N2 /H2 C2 H2 93:1:6 0.02 700–850 30 MWCNT 20–30 NA NA [156]
74 ␮m
Quartz 22 600 Quartz frit Fe-Mo 0.5–4.5 Al2 O3 NA 75–150 1 H2 CH4 NA 0.1 NA 650–700 800 MWCNT NA NA 4% [185]
Quartz NA NA NA Fe-Mo MgO Co-precipitation 0.1 Ar C2 H6 O 0.05–0.25 NA 850–950 30 SWCNT 0.8–1.8 [186]
Quartz 50 NA Quartz Fe 3 MgO NA NA 20 Ar CH4 75:25 4 NA 800 30 DWCNT 1.4–4 NA 98 [187]
Quartz 22 1000 Sintered Ni 5–60 Silica gel Impregnation 50 NA Ar CH4 1:1 1 760–860 20 SW/MW 0.9–1.35 12.5 [19]
quartz plate
Quartz 42 700 Sintered Mo-Fe Al2 O3 MOCVD 70 N2 /H2 C2 H2 11:1 1.2 650–850 40 MWCNT 10–50 60% 95 [188]
quartz plate
25 690 Porous Co-Mo 6 MCM-41 Impregnation 20–45 1 Ar CO 25:10 .35 800 30 SWCNT 1–2 [126]
plate 10
␮m
Quartz 30 475 Quartz Fe 8.4 MgO Impregnation 5–6 25 Ar/H2 Polyethylene/ 10:1 1 700–950 60–120 MWCNT 15–90 [128]
plate PCS
SS 110 N2 Polyolefin 0.4 m/s 0.05 450–850 MWCNT 15–40 85–90 [189]
20 Co-Mo 2 SiO2 Impregnation 5 H2 CO 1:99 2 700–850 30 SWCNT 0.6–1 [190]
NA NA NA Fe/Ru 0.3 Zeolite MOCVD 2–80 2 N2 /H2 C2 H2 12:6:1 0.05 0.03 700 MWCNT 9–44 38% [199]
SS 316 1000 SS grid Fe-Co Al2 O3 Impregnation 20–53 8 Ar C2 H6 O 1700:4 0.017 0.014 600 45 MWCNT 26 85 [200]
53 20 ␮m hole
Fe Floating catalyst 2 Ar C2 H2 6:5 800–1100 20 MWCNT 15–200 [201]
with
other
nano-
structure
Quartz 50 1300 Sintered Fe-Mo 10 Vermiculite Impregnation 10–100 5 Ar C2 H4 6:1 0.07 0.016 650 60 MWCNT 7–12 84 [202]
porous
plate
SS 310 80 SS mesh Fe/Ni 3–4 Al2 O3 Impregnation 100 50 N2 /H2 C2 H2 93:1:6 0.011 0.004 700–850 120 MWCNT 20–30 92% [203]
40 74 ␮m
SS 53 1000 Porous Fe/Co 5 Al2 O3 Impregnation 10–300 5 Ar C2 H6 O 1000:1 0.025–0.96 600 45 MWCNT 10–17 [204]
plate

859
860 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Fig. 21. Schematic mechanism of CNT agglomerate formation: (A) original catalyst particle; (B) the catalyst particle structure is crushed by CNT growth; (C) catalytic sites
are adequately separated and sub-agglomerates form; (D) fully developed agglomerates [175].

quartz or SS 304 or Inconel as per the literature. However, no effect
of material of construction on the quality and quantity of carbon
nanotubes has been reported.
Distributor plays an important role in fluidization. For synthesis
of CNTs researchers have used sintered porous plate, SS perforated
plate, SS grid etc. (See Table 3). However, additional details are not
available in the published literature regarding the design of distrib-
utor and the effect of distributor on the quality and quantity of the
product.
Some researchers [32,117] have used internals, whereas others
[98,118,119] have not used it. The internals affect the fluidization
behaviour of the particles; however, no details on this point regard-
ing CNT synthesis are available.
5.3. Effect of total gas flow rate
In a fluidized bed, two parameters namely, operating gas veloc-
ity (U) and minimum fluidization velocity (Umf ), are very important.
However, very few researchers have reported these two parame-
ters (see Table 3). Morancais et al. [118] showed the relationship
between U/Umf and MWCNT yield (Fig. 24). It appears that the
carbon yield tends to increase when U/Umf ratio decreases for a
similar amount of carbon introduced. This is certainly due to the
fact that the residence time of the gaseous precursor in the bed
increases with decreasing U/Umf . On the contrary, MWCNT forma-
tion decreased with increasing U/Umf . This report suggests, packed
bed is better than fluidized bed with respect to MWCNT yield.
However, studies by other authors do not support this observation.
Morancais et al. [118] pointed out that during the synthesis of CNTs,
Umf changed with time. It was roughly divided by a factor 6 after
120 min of run. This was due to the fact that with time the grain den-
sity sharply decreased due to low density carbon deposition; and
as a consequence, the fluidization ratio increased. In a recent paper
Liu et al. [120] depicted the effect of argon flow rate on synthesiz-
ing SWCNT. With increasing argon flow rate the amount of SWCNT
increased up to point and then decreased. They neither discussed

Table 4
Variation of CNT diameter with catalyst size.

Catalyst dia (nm) 3.2 ± (0.8) 9.0 ± (0.9) 12.6 ± (1.7) 1.7 ± (0.6) 4.7 ± (2.6) 1.9 ± (0.1) 1.0 ± (0.7) 3.7 ± (1.1)
CNT dia (nm) 2.6 ± (0.8) 7.3 ± (0.8) 11.7 ± (3.2) 1.0 ± (0.4) 2.9 ± (1.1) 1.0 ± (0.6) 1.1 ± (0.5) 3.0 ± (0.9)
Type of CNT SWCNT/DWCNT SWCNT/DWCNT MWCNT SWCNT SWCNT SWCNT SWCNT SWCNT
Ref [102] [102] [102] [193] [192] [194] [194] [99]
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
Fig. 22. Sequence of events of the growth of MWCNTs on the quartz substrate in a
continuous-feed CVD process: (A) random deposition of metal catalyst particles of
different diameters on the substrate, (B) nucleation of carbon nanotubes by diffu-
sion of carbon atoms into the deposited catalyst particles and further deposition of
catalyst particles, (C) random growth of MWCNTs via root-growth; catalyst parti-
cle enlargement leading to tube coarsening near rootend; catalyst particle-splitting,
(D) crowding of MWCNTs leading to vertical alignment; deposition of new particles
on the growing mat, part of catalyst carried away on the growing end of the tubes,
branching of tubes from catalyst particles that were carried away on growing end,
(E) MWCNTs grow by “tip-growth” from catalyst particles deposited on growing
nanotube mat; vertically aligned MWCNT-mat [176].
Fig. 23. Catalytic activities of selected metals for SWCNT/DWCNT production from
solid solutions of metal oxides – carbon source: CH4 , reaction duration: 6 min [114].
861
Fig. 24. Evolution with U/Umf of (A) carbon yield and fixed bed height, and (B) of
MWCNTs weight and formation rate [118].
the reason nor discussed the operating fluidization regime. See et al.
[119] found that the influence of U/Umf is insignificant in synthe-
sizing CNTs with respect to other parameters like temperature and
carbon precursor concentration.
In our opinion, the total gas flow rate will have an effect on the
yield of the CNT if the external mass transfer is the rate controlling
step.
5.4. Effect of carbon precursor and their partial pressure
The carbon source is one of the most important parameters
for synthesizing carbon nanotubes. For bulk production of car-
bon nanotubes, the precursor materials should be economically
attractive which can be easy to pyrolyze and avail in plenty. The
most common sources are hydrocarbon gases like methane, acety-
lene, ethylene, propylene, etc. (see Table 3). Researchers have also
used benzene [121], methanol [122], ethanol [123], camphor [25],
xylene [124], cyclohexane [125], carbon monoxide [126], lique-
fied petroleum gas [127], etc. Recently, Yen et al. [128] reported
that CNTs could be synthesized from solid-state polymers – poly-
carbosilane and polyethylene using FBCVD. Some authors found
a relationship between chemical structure of hydrocarbons and
CNT formation [122,129–136]. Hernadi et al. [130] have observed
that the unsaturated hydrocarbons have much higher yield and
deposition rate than the saturated ones. In addition, saturated car-
bon gases tend to produce highly graphitized filaments with fewer
walls compared to unsaturated gases. Consequently, they sug-
gested that saturated hydrocarbons are favored for SWCNTs growth
and unsaturated hydrocarbons for MWCNTs. However, SWCNTs
have been obtained from a highly diluted unsaturated hydrocarbon
[137–139]. Li et al. [132] demonstrated that the chemical struc-
ture of hydrocarbons, i.e., straight-chained ring or benzene-like
structures, is significantly more influential than the thermody-
namic properties (e.g., enthalpy) of the carbon source on the
type of CNT formation. Besides configuration, functional groups
862 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
Fig. 25. Effect of C2 H4 /H2 ratio on the MWCNT formation at (A) constant (B) variable
mass of carbon input [118].
of hydrocarbons have a decisive influence on the quality of the
produced material. The growth of clean SWCNTs was observed at
relatively low temperatures using alcohols with various catalysts
[122,139]. The authors concluded that alcohols are much better
carbon sources for SWNTs than hydrocarbons and this is likely
to be due to the ability attributed to OH− radicals to etch away
amorphous carbon deposits.
Carbon feeding rate obviously affects the reaction and hence
there is a critical flow rate for the process. Clearly at low flow rates,
there are not enough reactants to react with the catalyst, and the
carbon source concentration controls the rate of decomposition. A
higher flow rate increases the decomposition rate, however, after
a critical point, increasing the flow does not significantly affect
the decomposition rate or CNT growth. At that time CNT growth
is controlled by the catalyst particles availability. Single or multi-
wall carbon nanotubes growth, in fact, could be achieved by carbon
feeding rate control and any excess of carbon will result in dis-
ordered structures [140]. Cabero et al. [141] discussed influence
of acetylene partial pressure on carbon deposition at 700 ◦ C in
a hydrogen reaction mixture of 7% v/v in nitrogen atmosphere.
Carbon yield increased with increasing acetylene partial pressure.
There was partial deactivation of catalyst at high partial pressure
(17.5%) of acetylene. Morancais et al. [118] studied the influence
of C2 H4 /H2 ratio on the yield and the formation rate of MWC-
NTs. They varied C2 H4 /H2 between 0.11 and 0.66 in two distinct
studies. In the first one, the ethylene percentage and the run dura-
tion were varied simultaneously so as to operate with a constant
mass of introduced carbon. In the second one they fixed the run
duration for 120 min and varied the ethylene concentration. The
results are shown in Fig. 25. As per Fig. 25B when constant mass
of carbon introduced, the weight of MWCNTs increased with ethy-
lene till 25%, then decreased. However, the MWCNT formation rate
increased with increasing partial pressure of ethylene. On the other
hand when variable mass of carbon was introduced, both MWCNT
yield and its formation rate increased with ethylene partial pres-
sure as depicted in Fig. 25B.
5.5. Effect of temperature
Temperature plays an important role in each stage of CNT
growth. The temperature influences the morphology and the diam-
eter of CNTs, the growth rate of CNTs, and also the reaction
mechanism in the CVD process. Early literatures state that a very
high temperature (e.g., 1000–2000 ◦ C) favors the formation of SWC-
NTs over MWCNTs [129], however, with the advent of new CVD
methods, especially FBCVD, this opinion is changing as the SWCNT
growth temperature keeps getting lower [122,133,142,143]. Some
investigated conditions for the FBCVD growth of CNTs are displayed
in Table 3. Muataz et al. [144] pointed out that the MWCNT syn-
thesis occurs at temperatures greater than 500 ◦ C. However, the
maximum wall numbers with less impurity is obtained at 850 ◦ C
(see Fig. 26). Over this reaction temperature, more pronounced
is the formation of non-tubular carbon like nanofibers. They also
revealed a positive correlation between the average diameter and
the length of CNTs and temperature. As a result, they proposed that
the temperature is a dominating factor for CNT diameter control.
The same conclusions have been also reported by other researchers
[145–149]. For example, Lee et al. [150] observed an increase in
average CNT diameter from 20 nm to 150 nm as the tempera-
ture was increased from 800 ◦ C to 1100 ◦ C. Kumar and Ando [151]
reported an increase of CNT diameter from 8 nm to 26 nm with tem-
perature increase from 700 ◦ C to 900 ◦ C. However, there are some
inconsistencies about the exact effect of the temperature on CNTs
diameter. Kim et al. [146] did not observe any significant effects
of temperature on average diameter of MWCNTs but observed
that elevating the temperature had increased the length as well
as the crystallinity of the nanotubes. Son et al. [152] concluded
that the CNT diameters synthesized from methane in fluidized bed
decreased as the reaction temperature increased. Basically once the
nucleus is formed, the available carbon has three possible routes:
(1) the original cap can continue to grow to cover-up the catalyst
particle and deactivate it; (2) additional caps can form under the
old caps until the required diameter induces too much curvature
strain to make it energetically unfavourable; (3) carbon is added
to the cylindrical section of the tube. In our opinion, temperature
affects preferentially the above three steps either individually or in
combination depending on the system and thus gives rise to dif-
ferent morphology of the CNTs. Even though the higher growth
temperature is favored for less defective, well crystallized nan-
otube, with high yield and purity; but a too high temperature is
not suitable due to some disadvantages like deformation of cat-
alyst, sintering of the supported catalysts, formation of alloy in
bimetallic catalyst and the formation of pyrolytic amorphous car-
bon [136,145,153]. Indeed, it is likely that the size and shape of
the catalytic nanoparticles should be more stable at lower tem-
peratures, leading to better control of the size and chirality of the
nanotubes.
Fig. 27 depicts the influence of temperature on the carbon
yield, final fixed bed height, MWCNT weight and formation rate
at reported by Morancais et al. [118]. Maximum values were
obtained at 650 ◦ C. Above 650 ◦ C, the low values were due to deac-
tivation of the catalysts. The authors concluded that, in the first
stage of the process, MWCNTs growth induced an explosion of
the catalytic grains. Further MWCNTs growth generated significant
increase in fixed bed height and reduction in minimum fluidization
velocity. The temperature influenced significantly the porosime-
try properties of the MWCNTs. When the forces exerted by the
gas on particles became lower than the inter-particles forces, a
partial bed agglomeration occurred. The limiting step in this pro-
cess was the internal diffusion into the mesopores of alumina or
the MWCNTs. Recently, Philippe et al. [154] reported the changes
in the bed behaviour with temperature while synthesizing car-
bon nanotubes in a fluidized bed in the temperature range of
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869 863

Fig. 26. TEM images of carbon nanotubes at (A) 550 ◦ C, (B) 650 ◦ C and (C) 850 ◦ C [144].

550–750 ◦ C. A moderate bed agglomeration occurred at 700 ◦ C and 6. Commercial scenario

a more intense one at 750 ◦ C. In the 650–750 ◦ C range there was
no deactivation of catalyst, which was observed at 550 ◦ C and
600 ◦ C. The selectivity of the MWCNT formation was excellent at
650 ◦ C.
It is clear from the above discussion that in a fluidized bed tem-
perature affects the bed behaviour, the reaction mechanism and
thus the yield of the CNT produced along with the morphology and
diameter of CNTs in a very complicated manner, which still is not
fully understood. Further, the reactor geometry decides the flow
pattern. The temperature, particle sizes together with flow pattern
decide the yield and morphology of CNT.
A decade ago, carbon nanotubes were sold primarily in tiny
research quantities for hundreds or thousands of dollars per gram.
Highly purified or functionalized tubes still cost this much. How-
ever, as more companies have entered the market and production
levels grew, MWCNT prices have fallen to thousands of dol-
lars per kilogram. Recent market analyses by Freedonia Group
(http://www.freedoniagroup.com/Nanomaterials.html) and other
firms forecast sales of all nanotubes to reach $1 billion to $2 bil-
lion annually within the next 4–7 years. In terms of dollar value,
electronics devices will be the largest end-use category, although
composite materials in automotive applications may account for
greater volumes. These volumes are expected to approach several
thousand metric tons per year (see Table 5). Table 6 depicts pos-
sible commercial utilization of carbon nanotubes in different time
frames predicted by Freedonia study.
Hyperion Catalysis International of Cambridge, was the first
large-scale MWNT manufacturer and is now one of the largest,
with “tens of tons” of capacity. The company started producing
what it called carbon fibrils in 1983, patented its process in 1987,
and launched its first commercial application in 1991. In its more
than 20 years, Hyperion has seen small- and large-scale competi-
tors emerge; about 35 CNT suppliers can be found on supplier
lists. These include Bayer Materials Science (Germany), NanoLab
(U.S.A.), Nanocyl (Belgium), SouthWest Nanotechnology (U.S.A.),
Carbon Nanotechnologies Inc. (U.S.A.), Cnano Technology (U.S.A.,

Table 5
Potential market for CNT (www.freedoniagroup.com/Nanomaterials.html).

2004 2009 2014

Total demand (USD Millions) 6 215 1070

By type
Single-walled nanotubes 0 95 600
Multi-walled nanotubes 6 120 470

By end-use
Electronics 0 90 395
Automotive 1 31 165
Aerospace/Defence 0 10 65
Other 5 84 445

By region
U.S. 2 57 290
Western Europe 1 32 180
Asia/Pacific 3 113 500
Fig. 27. Influence of temperature on (A) carbon yield, fixed bed height (B) MWCNT
Other 0 13 100
weight, formation rate [118].
864 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869

Table 6
Possible commercial utilization of CNT in different time scale.

Current Short term Mid term Long-term

Conductive polymers and Sensors and instruments Coating (conducting thin films) Superconductor electrodes
composites (transportation, (microscope probes, tips, gas leak
electronics) detectors)
Catalysts (petrochemicals) Microwave antennas
Electromagnetic shielding Self-assembling yarns
Solar energy converters Aerospace (radar-absorbing skin)
Sporting goods (tennis racket)
Textiles and fibers Medical implants
Displays
Lithium ion batteries Drug delivery
Flat screen displays
Lamps
Semiconducting materials Circuits
Fuel cells
Advanced ceramics

China), Arkema (France), Iljin Nanotech (South Korea), Thomas & conditions, the process can selectively grow significant amounts
Swan Co. (U.K.), etc. of SWNT in less than an hour. The company promises to pro-
Bayer Materials Science is operating a pilot plant of annual duce specialty SWNT grades, priced at about $500 per g, having
capacities of 60 tons since 2007 at Laufenburg, Germany. A new ultrafine diameters and highly controlled chirality. It also will
plant of capacity 200 tons per annum is under construction. The make high-purity commercial grades with slight larger diame-
MWCNT, called Baytube (http://www.baytubes.com) is being pro- ters and broader chirality distributions for about $50 per g in
duced by fluidized bed CVD technique. Baytubes have found 1 kg quantities. Target markets for SWNTs include transparent
application in nano-dispersions, semi finished products made from electrodes in displays, photovoltaics, molecular wiring in energy
polyether ether ketone, polymer composite materials etc. applications, biosensors, drug delivery, and semiconductors. As
Cnano Technology (http://www.cnanotechnology.com) was companies expand and others enter the market, many observers
founded in 2007 with a plan to change the economics of nanotube suggest that prices for standard SWNTs could drop by a factor of
production and advance applications using extremely pure nan- 10.
otubes. Cnano has what it calls a “nano-agglomerate fluidized bed Carbon Nanotechnologies Inc. (CNI), the Houston based com-
technology” for low-cost MWNT production and a manufacturing pany was formed in 2000 by the late nanotechnology pioneer
site in China with a capacity of 500 tons per annum. Richard E. Smalley. He constructed a SWNT pilot plant. In 2005,
Among the leading large-scale producers, Nanocyl it also began offering double-walled nanotubes in up to kilo-
(http://www.nanocyl.com), started up a 15-kg-per-day CVD gram amounts. DWNTs behave similarly to SWNTs but have
reactor in 2005, and today it has an annual capacity of 40 tons for some unique properties and can be produced by CVD meth-
industrial, specialty, and research nanotubes. The company sells ods; CNI uses Smalley’s high-pressure CO (HiPCO) process for
industrial-grade MWNTs as liquid dispersions or epoxy and ther- SWNTs. Recently, Unidym (http://www.unidym.com), a devel-
moplastic solid forms. Earlier this year, it joined with the German oper of nanotube-based products for the electronics industry,
distribution company Velox to help increase its European market acquired CNI. The combination gives Unidym a large patent
presence. Nanocyl plans to ramp up its catalytic CVD process fur- estate for nanotube production and applications. The company’s
ther to meet growing demand. It opened a U.S. subsidiary in 2006 first product for the flat-panel display market is a transparent
and works in Asia through partners. It is also involved in several
European collaborations to develop applications, among them
Nanofire, targeting flame-retardant materials, and Nanohybrid, for
nanostructured polyolefin materials.
Nearly 5 years ago, Arkema (http://www.arkema.com) started
up a pilot-scale MWNT facility in Lacq, France, and now expanding
their production capacity to 400 tons per year. Arkema began by
selling nanotube powders made by catalytic CVD methods. Arkema
has a partnership with Zyvex Performance Materials, a Columbus,
Ohio, developer of nanomaterials. ZPM purchases single-, double-,
or multi-walled tubes and produces dispersed additives and con-
centrates for various applications. Its products are used by sport
equipment makers Aldila and Easton Sports, as well as by aerospace,
defence, health care, and electronics customers in a range of resin
systems.
Although SWNTs are not yet available in quantities near those
of MWNTs, the often more complex production process is being
scaled up by dedicated producers as well as those making a vari-
ety of tubes. For example, Nanocyl and the British firm Thomas
Swan offer both MWNTs and SWNTs. Swan launched its busi-
ness in 2004, using a CVD process developed with the University
of Cambridge. SouthWest Nanotechnology (SWeNT) uses a cat-
alytic CO disproportionation process, called CoMoCAT, developed
by University of Oklahoma. By optimizing the catalyst and reaction Fig. 28. Frequency of publications and patents on CNT.
 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
electrode to replace ones made of indium tin oxide. It is also
developing nanotube-based thin-film transistors for flexible elec-
tronics.
Despite the numerous applications reported to be making use
of CNTs, the production of CNTs has been low. CNTs are expen-
sive, ranging from US$ 35/g for MWNTs (NanoLab) to US$ 270/g
for SWNTs (Thomas Swan). It is expected that the price of CNTs
will drop to a viable level for use mass consumer products with
increased production capability, as has historically occurred for
other high-value materials, e.g., silicon wafers. Recently cost of
Baytube has come down drastically.
7. Conclusions
Scopus search on the frequency of publications and patents
on CNTs is shown in Fig. 28. However, these huge publications
and patents have not been translated into technologies for mass
production of carbon nanotubes in an economic way. The data
published so far are very much scattered, which is obvious from
Table 3. We understand that the fluidized bed CVD method has
the potential to deliver CNTs at an affordable rate. But for scale-
up, we need to understand the hydrodynamics, kinetics and mass
transfer of the bed during the process. Also we need to analyze
the forces which are acting between the particles and between
the particle and fluid. These aspects have not been addressed in a
proper way in the literature. Also we need to use cheap precursors
and minimize total numbers of steps involved in CNT produc-
tion. We have shown in our latest publication [177] that MWCNT
with high yield (19 times that of catalyst) and purity (96%) can be
obtained by pyrolyzing acetylene over carbon black using ferrocene
as catalyst. We have also seen in our laboratory that carbon black
can be fluidized in the nano-agglomerate form. We believe that
by using this substrate CNT can be produced at a much cheaper
rate.
In summary, we propose that further research into the synthe-
sis of CNTs is required in general, but especially in relation to the
FBCVD technique. In addition, we have highlighted the need for
integrating theoretical studies with empirical analyses to obtain an
optimal large-scale process, governed by fundamental science.
8. Suggestions for future work
For bulk production of carbon nanotubes in a fluidized bed we
need to understand the mechanism and kinetics of the overall pro-
cess as well as the hydrodynamics of the fluidized bed. A systematic
and rational approach will enable a reliable and economic scale-
up and the reactor design. Following are some suggestions for the
future work:
(1) The steps involved in fluidized bed CNT synthesis are given in
Section 4. A systematic experimental programme is needed to
find the rate controlling step(s) over a wide range of design and
operating parameters. This can be achieved by covering a wide
range of (a) supported catalyst- agglomerate size (b) pore size
within the agglomerate (c) superficial gas velocity (d) partial
pressure of hydrocarbon and hydrogen (e) voidage of emulsion
(f) radial and axial profiles of bubble phase and bubble size dis-
tribution (g) operating temperature (h) operating pressure (i)
column diameter (j) bed height (k) distributor design. Such a
comprehensive experimental programme will enable the esti-
mation of rate of reaction for each step given in Section 4. These
can then be suitably combined to get the overall rate of reaction.
(2) For the estimation of design parameters, the correlations used
for the conventional fluidized beds are unlikely to be useful
for the fluidization of nano-agglomerates. The future stud-
865
ies should include comprehensive experimental program to
measure the mass and heat transfer coefficients at various inter-
faces such as bubble-wake, bubble-emulsion, wake-emulsion,
particle-emulsion, bed wall-emulsion, etc.
(3) In comparison with conventional fluidized beds, the flu-
idization of nano-agglomerate offers many other challenges.
We need to understand particle–particle interaction and
the particle–fluid interaction. We need to understand the
mechanism of momentum and energy transfer across the
fluid–particle interface.
(4) The characteristics of bubbles in nano-fluidization are expected
to be different from those in conventional fluidized bed. An
extensive experimental program is required for the following:
(a) bubble size distribution in axial and radial direction
(b) measurement of drag and lift forces
(c) rates of coalescence and break-up need to be measured
under controlled conditions
(d) characterization of bubble generated turbulence
(e) measurement of axial and radial profiles of solid and gas-
phase fractions. It is known that the transverse distribution
of bubble hold-up has a decisive role in controlling the over-
all flow pattern in fluidized bed.
(5) The design of fluidized beds has been highly empirical because
of the complexity of hydrodynamics prevailing in fluidized
beds. It will be useful to make extensive measurements of:
(a) three dimensional mean flow pattern
(b) characterization of turbulence throughout the bed
(c) bed expansion characteristics and its relationship with the
flow pattern
(d) pressure drop characteristics and its relationship with flow
pattern.
(6) The modeling of process equipment has received attention
of researchers and practitioners using Computational Fluid
Dynamics (CFD). The CFD simulation of fluidized bed provides
several challenges. First of all, for validation of CFD simulations
we need experimental data mentioned under (4) and (5) above.
Secondly, the simulations need to include particle–particle
interactions using Discrete Elemental Method (DEM). Though
excellent attempts have been made in the past (see Section
2.5.1), substantial addition work is required to include:
(a) wide range of nano-agglomerates in terms of their proper-
ties
(b) improved formulation of drag and lift forces at bubble-
emulsion and solid–liquid interfaces. It will be useful to
model the particle–fluid and bubble–fluid interactions by
direct numerical simulation (DNS). This will enable the basic
understanding of the transfer of momentum, mass and heat
across the interfaces. As a result, these simulations will give
reliable procedures for the estimation of drag coefficient,
lift coefficient, mass and heat transfer coefficients across
particle–fluid and bubble–fluid interfaces. This micro-scale
modeling needs to be combined with macro-scale CFD mod-
eling for getting overall flow patterns. In this direction, some
attempts have been reported in the published literature
[79,205–211]
(c) incorporation of population balance model (PBM) along
with CFD and DEM with good description of break-up
and coalescence phenomena. The future work should also
include the characterization of flow and turbulent struc-
tures in fluidized beds. Some published work is expected
to be useful in this direction [212–219].
(7) The CFD–DEM–PBM should also include the understanding of
rate processes for the formation of CNTs as described under (1)
above.
(8) The transition from particulate to bubbling mode of fluidization
needs to be investigated theoretically and experimentally.
866 K. Dasgupta et al. / Chemical Engineering Journal 171 (2011) 841–869
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