Chemical Physics Letters 387 (2004) 307311 www.elsevier.

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CFD prediction of carbon nanotube production rate in a CVD reactor

Hajime Endo a, Kazunori Kuwana a,*, Kozo Saito Rodney Andrews b, Eric A. Grulke
a

a,* c

, Dali Qian b,

Department of Mechanical Engineering, University of Kentucky, 151 RGAN Building, Lexington, KY 40506-0503, USA b Center for Applied Energy Research, University of Kentucky, Lexington, KY 40511, USA c Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506, USA Received 10 June 2003; in nal form 27 January 2004 Published online: 10 March 2004

Abstract Chemical vapor deposition (CVD) is known as one of the most ecient methods of synthesizing carbon nanotubes. This Letter presents a computational uid dynamics (CFD) model to predict the production rate of nanotubes via catalytic decomposition of xylene in a CVD reactor. In our model, two gas-phase reactions and four surface reactions were considered. The rate constants of the surface reactions were determined using the inverse technique based on the measured tail gas concentrations. The predicted production rate agreed well with the experimental data, validating our model. 2004 Elsevier B.V. All rights reserved.

1. Introduction The production rate of nanotubes in a chemical vapor deposition (CVD) reactor depends on reaction conditions such as temperature, pressure, catalyst levels and morphology and reactant concentrations. These reaction conditions can vary throughout the CVD reactor. Modeling of these systems will provide important aids to the scientic understanding and engineering scale-up of these devices. In particular, computational uid dynamics (CFD) models should be helpful in interpreting nanotube growth rates, feedstock decomposition, byproduct compositions, transport rates and reaction mechanisms. There are numerous references reporting eects of reaction conditions (catalysts, alternative feedstocks and temperature are a few examples) on the production of single-walled and multi-walled carbon nanotubes [16], but few applications of CFD to the interpretation of reaction mechanisms.
Corresponding authors. Fax: +859-257-3304 (K. Kuwana). E-mail addresses: kuwana@engr.uky.edu (K. Kuwana), saito@ engr.uky.edu (K. Saito). 0009-2614/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2004.01.124
*

Research on the production and scale-up of vaporgrown carbon bers (VGCFs) in the 1990s addressed a number of similar issues. VGCFs have diameters in the range of $5 lm and lengths up to several millimeters. Fiber growth mechanisms are similar to those proposed for multi-walled carbon nanotubes. Researchers have studied the synthesis of the catalyst particles [7], nucleation and growth of carbon bers [811], the eect of the carbon source [12], the oating catalyst method [13,14], the eects of the substrate [15] and catalyst particle formation in the vapor-phase [16] and special pulse injection techniques to produce long bers [17]. These studies illustrate the importance that CFD could have for understanding the relationships between reactor operation and the product morphology. The production of long bers by the vapor-grown process requires stabilization of the gas ow and careful control of the mixing between the catalyst particles and the carbon source in the vapor-phase [17]. When substrates are used to support the catalysts, the mass transfer between the carbon source and the catalyst particles aects ber formation [15]. Some oating catalyst systems [14] produce straight bers when thermal convection is

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suppressed: CFD calculations demonstrated that laminar ow conditions, achieved with the use of a preheater section, were present when the best carbon bers were formed. These results provide further incentives for the application of CFD for improved interpretation of carbon nanotube production processes.

2. CFD model 2.1. Experimental method Fig. 1 shows a schematic of the University of Kentuckys CVD reactor [3,18]. This process can produce bulk quantities of high-purity well aligned multi-walled nanotubes through the catalytic decomposition of xylene. In our experiments, iron catalyst particles are rst deposited on the furnace walls through ferrocene decomposition. Following the catalyst deposition, xylene is supplied (3750 ppm) with carrier gas (argon with 10% hydrogen). Hydrogen scavenges for oxygen and prevents the loss of carbon to carbon dioxide. The reactor is batchwise with respect to catalyst, but continuous with respect to hydrocarbon feed. Xylene and carrier gas are preheated to avoid ow turbulence due to buoyancy. The Reynolds number in the reactor is $14, within the laminar ow region. The hydrocarbon concentrations in the tail gas are measured by mass spectra at dierent times, using a gas bag to transfer the tail gas to the mass spectrometer. 2.2. Reaction model A typical run to produce multi-walled carbon nanotubes takes two hours at the conditions used in this study. At the beginning, most of the xylene is converted to product. At the end of this period, only two-thirds of the xylene is converted and the run will be ended. At this point, the nanotube growth has been slowed, probably due to the formation of layered carbons on the process side of the catalyst nanoparticles. In this study, the kinetic analysis was done for one composition data set taken at 120 min. The apparent kinetic rate coecients determined for this data set do not include any catalyst

deactivation. Interpretation of catalyst deactivation will be done in a later work. Since xylene is the major carbon source for nanotube formation in our system, we neglect nanotube formation from ferrocene. Also, we assume that iron catalyst particles are uniformly distributed on the growth surfaces. Sinnott et al. [19] suggested a growth mechanism of nanotubes at catalyst surface: (1) adsorption of the carbon sources into the iron cluster with release of hydrogen; (2) diusion of carbon on and/or through iron particle; (3) precipitation of carbon as nanotube on iron surface. We now assume that the diusion rate in the iron/carbon system is at equilibrium and does not aect the concentrations in the gas-phase. Therefore, we can use a global rate equation for surface reaction of each carbon source. Analysis of the tail gas from our reactor shows the presence of toluene, benzene and methane as key reaction byproducts, with trace amounts of some C2 hydrocarbons [18]. This result indicates that xylene can decompose in the gas-phase as well as on the surface of the iron catalyst. As a working hypothesis, we include gas-phase decomposition of xylene to toluene, benzene and methane as well as decomposition to carbon and hydrogen of all four of these key reaction compounds at the catalyst surface. Based on above discussion, we consider the following gas-phase reactions: C8 H10 H2 ! C7 H8 CH4 C7 H8 H2 ! C6 H6 CH4 and surface reactions: C8 H10 ! 8Cnanotube 5H2 C7 H8 ! 7Cnanotube 4H2 C6 H6 ! 6Cnanotube 3H2 CH4 ! Cnanotube 2H2 r3 kBTX CX r4 kBTX CT r5 kBTX CB r6 kM CM R3 R4 R5 R6
0:5 r1 k1 CX CH 0:5 r2 k2 CT CH

R1 R2

y
Preheater, 513 K Furnace, 973 K

Ar/H2, 300 K

z
Gas outlet

Xylene

Fig. 1. A schematic of the CVD reactor.

where subscripts B, T, X, M and H denote benzene, toluene, xylene, methane and hydrogen, respectively. The rate constants obtained by Benson and Shaw [20] are used for gas-phase reactions (R1) and (R2). The rate constants of surface reactions (R3)(R6) need to be determined based on our tail gas analysis. In the present model, the same rate constant, kBTX , is assumed for arenes because of their similar molecular structure. Eqs. (R1)(R6) represent a simple reaction mechanism scheme appropriate as a rst step to understanding the CVD synthesis of carbon nanotubes. The surface reaction rate expressions, (R3)(R6), could be substituted by other, more detailed equations (LangmuirHinschelwood equations, for example) as more information about the surface adsorption and reaction processes is discovered.

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2.3. Rate constants of surface reactions Since the temperature of growth surfaces is uniform and constant (being controlled by the furnace), both kBTX and kM can be treated as temperature independent constant. The reaction rate constants, kBTX and kM , can be obtained by an inverse CFD calculation based on measured tail gas concentrations. Using the tail-gas concentrations, two unknown parameters (kBTX and kM are determined via minimization of the function: i2 Xh c m Ci;out kBTX ; kM Ci;out ; EkBTX ; kM
i

i C8 H10 ; C7 H8 ; C6 H6 ; CH4 ;

c where Ci;out is the calculated tail-gas concentration of m species i, which is a function of kBTX and kM , and Ci;out is the measured tail-gas concentration.

2.4. Fluid dynamics model The uid dynamics model adopted here is based on 3D, laminar and steady state ow with both gas-phase and surface chemical reactions. The conservation equations of mass, momentum, energy and species are solved with the aid of the ideal gas law. Physical properties (viscosity, thermal conductivity and specic heat capacity) of each species are assumed temperature dependent [21] and those of the gas mixture are calculated according to the mixing law.

There is a signicant amount of decomposition of xylene in the gas-phase. If no surface reaction were present, the exit concentration of xylene would be 3085 ppm, as shown in Table 1, for a conversion of 17.7%. This decomposition would generate 627 ppm toluene, 27 ppm benzene, and 700 ppm methane. The presence of the surface reaction reduces the levels of all the hydrocarbons. Fig. 2a shows vertical distributions of temperature and axial velocity in the preheater. The feed gases enter in a jet-like fashion and induce a backow near the wall. Also, there is a lower temperature region at the center due to the inlet condition. In the furnace, on the other hand, temperature and axial velocity distributions are uniform as shown in Fig. 2b, indicating a laminar ow region in the furnace (a favorable condition for producing nanotubes). Fig. 2 illustrates the importance of CFD modeling. In our system, operational changes in the feed gas condition and preheater temperature are known to aect nanotube production rates. The importance of ow in the region close to the inlet and the temperature of the feed gases has already been noted qualitatively by several researchers [17]. Clearly, knowledge of the temperature, concentration and velocity proles throughout the reactor will be needed to link the local chemical processes with the uid dynamics and to provide the best description of the process.

3. Results and discussion From the inverse calculation, the following rate constants, kBTX and kM , of the surface reactions (R3) (R6) were obtained: kBTX 3:4 104 m s1 at 973 K; kM 8 103 m s1 at 973 K: 2 3

The calculated and measured tail gas concentrations are in good agreement as shown in Table 1. Xylene, toluene and benzene concentrations have small dierences between calculated and measured values, because the same rate constant is assumed for surface reactions of these species.

Table 1 Tail gas concentrations Species C8 H10 C7 H8 C6 H6 CH4 Measured (vol ppm) 1234 172 4 38 Calculated (vol ppm) 1230 249 11 38 Calculated (no surface reaction) (vol ppm) 3085 627 27 700

Fig. 2. Vertical distributions of temperature and axial velocity in: (a) preheater; (b) furnace.

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10000 Concentration [vol ppm] 1000 100 10 1 0 C8H10 C7H8 C6H6 CH 4

Total production rate [mg h 1]

Preheater

Furnace

400 300 200 100 0 0 Measured Predicted

0.5 1 z distance [m]

1.5

1000 2000 3000 4000 Inlet xylene concentration [vol ppm]

Fig. 5. Calculated and measured total production rates.

Fig. 3. Axial concentration distributions of xylene, toluene, benzene, and methane along z axis (centerline).

Fig. 3 shows axial concentration distributions of xylene, toluene, benzene and methane along the z axis. Xylene starts to decompose at the entrance of furnace (z $ 0:6 m) and its concentration decreases with an increase of z. Both toluene and methane concentrations rapidly increase in close stoichiometric ratios over z 0:60:7 m. Over z 0:71:5 m, the toluene concentration slowly increases, while the methane concentration slowly decreases. At z 0:7 m, where the toluene is produced at a signicant level, benzene is produced and its concentration keeps increasing with an increase of z. Fig. 4 shows an average nanotube deposition rate over a cross-sectional area along the z axis for the inlet xylene concentrations, IXC: 938, 1875, 2812 and 3750 (baseline case) ppm. The nanotube deposition rate for all four cases decreases with the increase of z; the trend is similar to the decrease of xylene concentration shown in Fig. 3. The rate constants shown in Eqs. (2) and (3) were used for all four cases. In our experiments, the maximum deposition rate was achieved at the entrance to the fur-

nace and the deposition rate decreases with an increase in the axial distance, similar to that predicted in Fig. 4. Total production rate of nanotubes can be calculated by integrating the local deposition rate over the growth surfaces. The total production rate for four dierent inlet xylene concentration cases, as shown in Fig. 4, was calculated and shown in Fig. 5. After the contribution of ferrocene was subtracted from the experimental data, the measured values for the inlet xylene concentrations (of 3750 and 1875 ppm each) match the corresponding prediction with an accuracy of better than 90%. The proposed simple CFD model is sucient to describe the reaction products observed in the exhaust gas while correlating with the amount of nanotubes grown.

4. Conclusion Our CFD model predicted uniform velocity and temperature distributions in the furnace region, a favorable condition for producing uniform quality nanotubes. The predicted concentration distributions are those expected for reactions in series. Calculated total production rate of nanotubes is favorably compared to the measurement with 90% agreement, indicating the proposed two-step gas-phase and four-step surface reactions to be reasonably accurate to predict the nanotube production rate.

Deposition rate [mgc m 2h 1]

0.6 0.5 0.4 0.3 0.2 0.1 0

375 0 ppm

281 2

ppm

1875 ppm

Acknowledgements This work was funded by NSF MRSEC Grant DMR-9809686.

IXC = 93 8 ppm

0.6

0.8

1 1.2 z distance [m]

1.4
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Fig. 4. Axial distribution of average deposition rate at the furnace walls for four dierent inlet xylene concentrations (IXC).

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