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Critical review of the paper: "Kinetic modeling study of carbon nanotubes synthesis by fluidized bed chemical vapor deposition"

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CARBON NANOTUBES

SYNTHESIS BY FLUIDIZED BED

CHEMICAL VAPOR DEPOSITION

ARTICLE CRITICAL REVIEW

THE AUTHORS

Toulouse Cedex 4, France ARKEMA LACQ Research Center, 64170 Lacq, France

P. Serp and Ph. Kalck LCC/ENSIACET/INPT, UPR CNRS 8241, Toulouse University,

31077 Toulouse Cedex 4, France

S. Borde`re, D. Plee, and P. Gaillard ARKEMA LACQ Research Center, 64170 Lacq,

France D. Bernard ARKEMA, 92705 Colombes Cedex, France

B. Caussat LGC/ENSIACET/INPT, UMR CNRS 5503, 31106 Toulouse Cedex 1, France

ABOUT THE PAPER

Engineers AIChE J.

Vol: 55

Pages: 465-474

Month: February

Year: 2009

STATEMENT OF THE PROBLEM

The authors present an implementation of the kinetic and physical laws developed in a

previous study; in a modified version of the bubbling bed Kato and Wen model to

represent multiwalled carbon nanotubes (MWCNTs) synthesis by catalytic chemical

vapor deposition from ethylene as carbon source and using an Fe/Al2O3 catalyst. In

addition, study the influence of the main operating parameters on the evolutions with

time of the species molar fractions, the weight of MWCNTs formed, and the bed

characteristics; can help designing new reactors.

NOTATION

RESULTS FROM PREVIOUS WORK / APARENT

KINETIC EQUATIONS

The chemical mechanism used to describe the decomposition of ethylene and the

formation of MWCNTs is composed of three apparent catalytic reactions:

RESULTS FROM PREVIOUS WORK / APARENT

KINETIC EQUATIONS

The kinetics laws for each reaction presented before is like follow:

RESULTS FROM PREVIOUS WORK / PHYSICAL LAWS

ABOUT THE EVOLUTION OF THE BED

In this point the paper present some problems, thus:

The paper say that In the rst part of the study, we have determined the evolution of the

main physical parameters of the FB, i.e., mean volume diameter of powders, apparent

grain density, xed bed height, and minimum uidization velocity, with run duration. This

analysis isnt in the part 1 mentioned.

The paper say that It appeared that the discrepancy between these two sets of values

was in average of 15%. As a consequence, the model presents an intrinsic error of about

15% due to these physical laws of evolution. this affirmation is not clear and is been

responsible of the 15% of the difference between the model and the experimental data.

RESULTS FROM PREVIOUS

WORK / PHYSICAL LAWS

ABOUT THE EVOLUTION

OF THE BED

the fluidized bed and of the

particles features with X1 the

MWCNTs productivity. (a)

Fixed bed height, (b) average

diameter of particles, (c)

apparent density, and (d)

minimum fluidization gas

velocity.

RESULTS FROM PREVIOUS WORK / PHYSICAL LAWS

ABOUT THE EVOLUTION OF THE BED

Analysing the data the Authors say that the evolutions of dp and qp lead to a decrease of

the minimum uidization velocity between 0 and 0.4 gC/gcata and then to an increase of

Umf until values higher than its initial value, for 2.7 gC/gcata.

This is just an observation from the graphs, but could be necessary to understand the

behavior, to relate the Umf with the bed height.

PRESENTATION OF THE

MODEL

Representation of a fluidized bed according

to Kato and Wen, work Blubble assemblage

model for fluidized bed catalytic reactor.

THE ASSUMPTIONS

It is represented by a series of compartments whose height is equal to the mean

diameter of bubbles at the corresponding level.

THE ASSUMPTIONS

Bubbles are growing by coalescence as they ascend through the bed; the bubble diameter is

given by the empirical relation of Kobayashi:

Where

The number of holes of the distributor per surface area of column b0 is equal to 30 cm-2 for

the analyzed case.

THE ASSUMPTIONS

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

of Davidson and Harrison.

Where

THE ASSUMPTIONS

Each compartment is constituted of two phases, the bubble one corresponding to the

bubbles and their cloud, and the emulsion one, in which wakes are included; the volume

of the bubbles for the kth compartment is given by:

Where

And the resulting volume of the emulsion for the kth compartment is given by:

THE ASSUMPTIONS

The convective mass transfer in the emulsion phase is neglected.

In each compartment, mass transfer occurs between the two phases and the exchange

coefficient is given by the Kobayashi correlation:

THE ASSUMPTIONS

A final assumption was made about the slugging regime, and was, that it is reached when

the bubble diameter is equal or higher than a limit value corresponding either to the

diameter given by the relation of Grace, if this value is lower than 0.8 times the reactor

diameter.

When the slugging regime occurred, the authors arbitrarily fixed the bubble diameter to

this value to perform the calculations, but the final results were clearly less precise.

MODIFFICATION TO THE MODEL OF KATO AND

WEN

Considering the stoichiometric of the reactions, the authors have modified the mass

balance equations of the model to consider the influence of variations of gas flow rate

induced by chemical reactions, and say that; Indeed, experimentally a nonnegligible

increase of the total flow rate has been observed by Gas Chromatography during

MWCNT synthesis.

MODIFFICATION TO THE MODEL OF KATO AND

WEN

The modified mass balances equations are the following:

For the bubble phase:

MODIFFICATION TO THE MODEL OF KATO AND

WEN

Where the parameter qEB quantifies the gaseous flux transferred from the emulsion to

the bubble phase, per unit volume of bubble and is equal to:

MODIFFICATION TO THE MODEL OF KATO AND

WEN

Which allows to obtain the evolution of the superficial gas velocity U from a

compartment to another, thus:

RESULTS AND

DISCUSSION

Experimental and Simulated

Results

RESULTS AND DISCUSSION

productivities (runs Cin1 to Cin25). (a) X1

MWCNTs productivity, (b) X2 ethane

productivity, and (c) X3 methane productivity.

RESULTS AND

DISCUSSION

Comparison between

experimental and simulated

(a) fixed bed height and (b)

average particle diameter.

RESULTS AND

DISCUSSION

After, the authors present the spatial

and temporal evolutions of some

process parameters, thus:

Axial evolution of ethylene and

hydrogen molar fractions in each

phase for various run durations

under the conditions of run Cin3. (a)

Ethylene molar fraction in the bubble

phase, (b) hydrogen molar fraction in

the bubble phase, (c) ethylene molar

fraction in the emulsion phase, and

(d) hydrogen molar fraction in the

emulsion phase.

RESULTS AND

DISCUSSION

Simulated evolution of (a) the

fluidization ratio U0/Umf and

(b) the expanded bed height

with run duration for various

temperatures.

Simulated evolution of

MWCNTs weight with run

duration for various

temperatures.

RESULTS AND

DISCUSSION

Influence of the inlet molar

fraction of ethylene on (a) the

ethylene conversion rate and

(b) the final mass of

MWCNTs for various

temperatures.

RESULTS AND

DISCUSSION

Influence of the inlet molar

fraction of ethylene on (a) the

final expanded bed height and

(b) the mean grain diameter

for various temperatures.

RESULTS AND

DISCUSSION

Simulation of Various Process

Scale Up.

It is worth noting that the

slugging regime never occurred

for these simulations since the

ratio between the final fixed

bed height and the reactor

diameter H/D never exceeded

3.2. This strengthens the validity

of these predictions.

CONCLUSIONS OF THE ARTICLE

A model of fluidized bed has been developed to represent MWCNTs synthesis by Catalytic Chemical Vapor

Deposition from ethylene as carbon source and using an Fe/Al2O3 catalyst. The kinetic and physical laws

developed in Part 1 have thus been implemented in a modified version of the Kato and Wen model.

To the best of our knowledge, this is the first time that a two-phase bubbling bed model is used to simulate a

viable process of large scale MWCNTs production.

Its domain of validity is of course restricted to the operating range used to develop the associated kinetic and

physical laws. Its accuracy is also limited by the fact that the kinetic laws are not intrinsic and do not account

for any deactivation phenomenon.

The absolute deviation for MWCNT productivity between these experimental results and the simulations was

of 20.8% for the whole data and of 17.3% when considering only experiments for which the bed was mainly in

bubbling regime.

CONCLUSIONS OF THE ARTICLE

A perspective of the work could then be to implement these kinetic and physical laws in a

slugging bed model11 or in an Eulerian multifluid model-like MFIX12 to better represent the

hydrodynamics of the fluidized bed in particular in slugging regime and the associated

interphase mass transfers.

The code has also allowed to calculate the influence of the main operating parameters on the

evolutions of the species molar fractions and on the bed characteristics vs. run duration.

This numerical tool can then help to better control the evolution with time of the process

behavior, for instance, in terms of fluidization regime, mean diameter of grains, or expanded

bed height. In a last part, the influence of the bed features as the reactor diameter and weight

of catalyst has also been studied proving the interest of such model for scale up.

CONCLUSIONS OF THE ARTICLE

Simulations have shown that the productivity in MWCNTs could reach 8 kg/h in a 45-cm

diameter reactor operating in semi-batch conditions. This corresponds to around 74

tons/year of MWCNTs selectively produced.

An increase of reactor diameter provides better interphase contacts due to lower bubble

diameters, relatively to reactor diameter, and then enhances the process productivity in

MWCNTs and its selectivity regarding ethane and methane. The interest of the process

to massively produce MWCNTs is then fully demonstrated.

GENERAL DISCUSSION ABOUT THE ARTICLE

Analyzing the results and the conclusions presented by the authors, I can say that in the

article there is coherency and the information presented were evaluated carefully; there

are some point in which could be missing information, but all the analyses seems to be

ok.

The work was focused on the comparison between the modeling and the experimental

data, which correspond with the purpose of the article, but could have present and take

advantage of the data to present more details about the phenomena; or use it to explain,

in a more detailed way, the behavior of some variables.

GENERAL DISCUSSION ABOUT THE ARTICLE

The title of the article was appropriate and clear about the topics on it, the abstract was

specific, representative of the article, and was presented in the correct form; and with the

introduction let know to the reader the purpose of the work.

I consider that whole the discussion raised in this paper, was relevant and very important

for the development of the technique of mass production of multiwall carbon nanotubes,

like a very important material for the futures developments.

THANKS

ANDRS FELIPE MUOZ PATIO

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