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A Numerical Model of Silane Pyrolysis in a Gas-Solids Fluidized Bed

Article · January 2001

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 A numerical model of silane pyrolysis in a
gas-solids fluidized bed
C. Guenther †
Fluent Incorporated, Morgantown, WV
T. O’Brien
National Energy Technology Laboratory, Morgantown, WV
M. Syamlal
Fluent Incorporated, Morgantown, WV

Abstract
Recent experiments have shown that silane pyrolysis in a gas-solids fluidized bed may be
an attractive way to produce ultra-pure silicon. Such a process would possess the general
advantages of fluidized bed technology, namely, good contacting, thermal homogeneity,
thorough mixing of particles, easy solids handling, and low pressure drop.
Such a fluidized bed reactor is simulated using the two-fluid hydrodynamic model MFIX
(Multiphase Flow with Interphase eXchanges; www.mfix.org), developed at the National
Energy Technology Laboratory. Using MFIX three-dimensional simulations of silane
pyrolysis are performed. The chemistry is described by a simple set of homogeneous
and heterogeneous reactions. Results are compared to available experimental data where
silicon deposition rates on a bed of alumina particles were measured as a function of
temperature, bed height, and fluidization velocity.
Keywords: ultra-pure silicon; silane pyrolysis; fluidized bed; two-fluid model; reactive fluidized
bed


This research was supported by the DOE-OIT Chemical Industries of the Future, administered
through Oak Ridge Institute for Science and Education under the direction of Dr.Thomas O’Brien.
†
Correspondence to: Fluent Inc., 3647 Collins Ferry Road, Morgantown, WV 26505, E-Mail:
cpg@fluent.com

1
1 Introduction
Although silicon is the second most abundant element in the Earth’s crust, exceeded only
by oxygen, it is quite reactive and is only found naturally in an oxidized form, silicon
dioxide (as crystalline or amorphous minerals) or in the more abundant and wide-spread
silicates. To produce commercial silicon (Si), silicon dioxide (SiO2 ) is reduced by reac-
tion with coke in large electric furnaces to produce an impure elemental product. This
metallurgical grade Si requires further refinement to meet industrial needs, especially the
demand for ultra-pure silicon in the microelectronic and solar industries.
The conventional Siemens process for the production of ultra-pure silicon involves the
reduction of silicon tetrachloride (SiCl4 ) or trichlorosilane (SiHCl3 ) by hydrogen (H2 ).
The product, silicon, is deposited on hot (T  1150oC) filaments. Despite the popularity
of this approach there are several obvious disadvantages, that include batch operation,
high energy requirements, and harsh byproducts. Alternative approaches, using fluidized
bed technology, have been suggested by [1]-[4]. In these approaches silane (SiH4 ) is py-
rolyzed in a fluidized bed and silicon is deposited onto the surface of bed particles. Some
of the advantages of this process over the traditional route are lower energy consumption,
easy solids handling, continuous operation, and the absence of harsh byproducts.
Currently, as with all fluidized bed processes, there are no well established methods
for scale-up. The design of fluidized bed reactors is usually based on a collection of
empirical correlations which quantify concepts such as the minimum fluidization veloc-
ity, bed expansion, and ”bubble” properties. These correlations were derived from many
man-years of experimental study of fluidized beds ([5]-[6]). However, it is still difficult
to integrate this information into a comprehensive model of fluidized beds because of
the inability to predict these quantities accurately and to analyze their interactions. This
becomes especially difficult for models which attempt to predict, not only bed dynam-
ics, but also heat transfer and chemical reactions. Recently, [7] and [8] modified several
of the classical fluidization models found in the literature to include the variation of gas
flow-rate due to chemical reactions. However, these new models only considered mass
transfer between a single spherical bubble and the emulsion phase, neglecting the more
complex features inherent to fluidized beds such as complex mixing, bubbles splitting and
coalescing, and gas-solids circulation rates and patterns. Bubbles (regions with very few
particles), significantly affect reactor performance; the motion of these voids maintains
uniform bed temperature and promotes mixing, although this allows reactant bypassing.
So, it is essential for models of fluidized bed processes to accurately predict bubble char-
acteristics and transient behavior.
In this paper an alternative method for simulating fluidized bed reactors is presented
using the two-fluid hydrodynamic model MFIX (Multiphase Flow with Interphase eX-
changes; www.mfix.org) developed at the National Energy Technology Laboratory [9].
The idea of describing fluidized beds with two-fluid hydrodynamic models has existed

2
since the early 60’s ([10]-[12]). The resulting equations set forth by these researchers
are very difficult to solve, and numerical solutions that predict bubbles came much later
([13]-[19]). These studies, as well as the majority of other numerical investigations, were
restricted to two-dimensions because of computational costs. Three-dimensional studies
using two-fluid models are rarely found in the literature and the few that do generally
use very low-order spatial discretization techniques such as first-order upwinding (FOU)
to improve convergence. Unfortunately, this type of approach is typically unsatisfactory
because of the large amount of numerical diffusion inherent to FOU [19]. One of the
primary objectives of this paper is to demonstrate the importance of conducting high-
order three-dimensional simulations especially when chemical reactions are present and
explicit tracking of species concentrations is required. This paper begins with details of
the physical models and numerical techniques used in the simulations. Grid independence
is established which is essential to ensure the bed hydrodynamics predicted by MFIX is
the true solution of the governing equations. With grid independent simulation results, a
global reaction kinetics scheme [3] and a more detailed scheme [4], are compared with
experimental data of [4] where silicon deposition rates on a bed of alumina particles were
measured as a function of temperature, bed height, and fluidization velocity.

2 Mathematical Model
2.1 Two-Fluid Model
Two-fluid hydrodynamic models, also referred to as Eulerian-Eulerian models, treat the
fluid and solids as two continuous and fully interpenetrating phases. This approach results
in mass, momentum, and energy balance equations for both the gas and solids phases. For
isothermal conditions, the continuity, momentum balance, and species balance equations
for two phases (gas and solids) with chemical reactions are given below.

Gas-phase continuity
∂   Ng

∂t
εg ρg  ∇  εg ρg v g 
∑ Rgn (1)
n 1
Solids-phase continuity

∂   Ns

∂t
εs ρs  ∇  εs ρs v s  ∑ Rsn (2)
n 1

Gas-phase momentum
∂   
εg ρg v g  ∇  εg ρg v g v g   εg ∇Pg  ∇  τ̄¯ g  Fgs v s v g 
∂t

3
  
εg ρg g  R0  ξ0 v s ξ̄0 v g  (3)

Solids-phase momentum

∂  
εs ρs v s  ∇  εsρs v s v s   εs ∇Pg ∇  S̄¯ s  Fgs v s  v g 
∂t   
 
εs ρs g  R0  ξ0 v g ξ̄0 v s  (4)

Species balance
∂ 
εm ρm Xmn  ∇  εm ρm Xmn v m  Rmn (5)
∂t  
where m  g s  for the gas(solids) phase and ξ̄0  1  ξ0 and ξ0  1 if R0  0; else

ξ0  0. The eight dependent hydrodynamic variables in 3D: void fraction εg (the solids
fraction εs  1  εg ), pressure Pg , and six velocity components are found by using MFIX
to numerically solve the coupled non-linear partial differential equations (1)-(5). The
number of species mass fractions (Xmn ) tracked are given in Section 4.1. Constitutive
relations, needed to close the system (1)-(4), can be found in [9].

3 Numerical Procedure
The governing set of partial differential equations (1)-(5) are solved on the computational
domain with a finite number of cells or control volumes [20]. Nodal points are located at
cell centers where scalars (pressure, voidage, etc.) are stored. Velocities are defined at cell
faces by using a staggered grid [21]. The finite volume method integrates the equations
over each cell which, for a general property φ , produces a discretized set of equations of
the form

aP φP  ∑ anb φnb SP (6)
nb

where the P is the nodal point and the subscript nb represent contributions from surround-
ing cell faces. The partial elimination algorithm [22] is used to uncouple the discretized
momentum equations due to the gas-solids drag. Using an extension of SIMPLE [21], a
sequential iterative procedure is used to solve (6) and a solids volume fraction correction
equation [20] adjust velocities in order to satisfy conservation of mass in both phases.
One of the key features of the finite volume method is the need to calculate convec-
tive fluxes at cell faces. Recent investigations [19] have shown that this step is crucial
for accurately predicting bubble dynamics. To summarize this important point, [19] used
the universal limiter [23] and deferred correction [24] to implement high-order approxi-
mation of cell face contributions. The universal limiter prevents non-physical numerical
oscillations; the deferred correction method retains the desirable stability properties of a
low order method, in this paper first-order upwinding (FOU), to form the algebraic system

4
given by (6). In this paper high-order cell face fluxes were approximated using the Super-
bee method. Superbee was chosen because of its superior performance over other second
order methods [19]. To capture the resolution of a higher order method an additional
source term is added
aP φP  ∑ anb φnb  SP  SDC  (7)
nb
The additional source term is given by

SDC ! εm ρm " f vm " f φ LO # φ HO " f A f (8)

where A f is the area of the cell face f and the subscript m  g(s) for the gas(solids) phase.
Equation (7) is derived by adding and subtracting FOU convection terms to the higher
order convection terms. The difference between the higher order convection terms and
the FOU convection terms are combined to form the source term SDC . The added FOU
convection term appears implicitly in the coefficients aP and anb . Since the added and
subtracted FOU convection term cancel out, at convergence there is no net contribution to
equation (7) from φ LO . Therefore, at convergence the discretization used in equation (7)
is purely higher order.

4 Experimental and Numerical Results

The reaction vessel used in the experiments is a 5.3 cm (ID), 63 cm long, stainless steel
cylinder, surmounted by a 11.2 sloping transition section, joined to a 17.7 cm tall expan-
sion zone [4]. A mixture of silane (SiH4 ) and nitrogen (N2 ) is introduced into the reactor
through a stainless steel perforated plate distributor. Gases exit the reactor through a 2 cm
(ID) tube in the center of the top plate.
In the experiments of [4], alumina particles (Al2 O3 ) were employed as seed particles,
rather than ultra-pure silicon particles, claiming that this change in the nature of the seed
particles did not affect the deposition process. The average size of the particles is 82 µ m
with a density of 3.9 g/cm3 and a minimum fluidization velocity of 1.3 cm/s.

4.1 Chemical Model

In this paper two chemical schemes have been implemented to describe the chemistry of
the pyrolysis of silane. The first is a global scheme corresponding to the following overall
reaction

SiH4 $ Si+2H2

where two gas species (SiH4 , H2 ), and two solids species, (Si, Al2 O3 ), were tracked using
(5). Reaction mechanisms for the kinetics can be found in [3]. In addition to this global

5
mechanism, a more detailed description of the chemistry was considered, initiated by the
reversible, homogeneous reaction

SiH4 % SiH2 +H2 .

The highly reactive silylene (SiH2 ) can participate in a series of reactions to form higher
order silanes. In this paper we only consider the homogeneous reaction to form disilane
(Si2 H6 )

SiH2 +SiH4 % Si2 H6 .

Heterogeneous decomposition of SiH4 and SiH2 is described by the irreversible reactions;

SiH4 & Si(s)+2H2 , SiH2 & Si(s)+H2 .

For these reactions four gas species (SiH4 , H2 , SiH2 , and Si2 H6 ), and two solid species
(Si, Al2 O3 ), were tracked. Details of this reaction mechanisms can be found in [3] and
[4].

4.2 Grid Independence and MFIX Results

In order to establish grid independent solutions several simulations were performed ne-
glecting chemical reactions. The number of cells was kept constant in the radial and
axial directions with 25 and 80 cells respectively, which has been determined to be grid
independent in two-dimensions. Beginning with a 2-dimensional simulation with sym-
metry, the number of cells was incrementally increased in the azimuthal or z-direction.
To demonstrate the importance of using high-order methods, a single simulation using
first-order upwinding (FOU) was included. For this simulation 24 cells in the z-direction
were used. Simulations were run for 3.6 seconds and time averaged over the final 2.6
seconds of each run. Because of the chaotic nature of fluidized beds we use the term ”grid
independence” as a qualitative measure for determining when grid independent average
bed behavior has been reached rather than a point to point convergence criteria. Figure
1 shows the axial profiles of the solids volume fraction averaged over both time and the
radial direction. Clearly, a qualitative change in the bed expansion occurs when the res-
olution of the higher-order simulations are increased from 4 to 12 z-cells. However, the
FOU over predicts the bed expansion despite the increased resolution in the z-direction.
According to this measure the calculation has converged with 12 z-cells using the higher
order method. Voidage profiles are shown in Figures 2 and 3 as a function of radial po-
sition, averaged over different horizontal sections of the bed. Again, a qualitative change
in the profiles is clear as the grid is refined from 4 z-cells to 12 z-cells and grid indepen-
dence is reached with 24 z-cells. In the transient results voids or bubbles which form at
the bottom of the bed migrate towards the center of the reactor as they travel upwards.

6
 60
2-D
FOU
4 z-cells
Height (cm)

40 12 z-cells
24 z-cells
36 z-cells
20

0
0 0.25 0.5 0.75 1
Solids Volume Fraction

Figure 1: Axial Profile of the Solids Volume Fraction.

7
 0.68 0.68

0.64 0.64

Voidage

Voidage
' 0.6 ' 0.6

0.56 0.56

0.52 0.52
0 1 2 3 0 1 2 3
Radius (cm) Radius (cm)

Figure 2: Radial Voidage Profiles Averaged Over Time and the Heights 2-10 cm
and 10-20 cm.

This behavior is shown in Figures 2 and 3. On the other hand, the 2-D simulation and
FOU both predict very different qualitative behavior i ( e ( , higher voidage away from the
center of the bed and significant under prediction of the solids concentration at the wall in
the lower regions of the bed.
The results using MFIX to model silane pyrolysis in a gas-solids fluidized bed are
presented using the Superbee method with 24 cells in the z-direction. Due to the limited
space available only the results of run S5 will be shown . Figures 4 and 5 show the gas
phase mass fractions for run S5 using the detailed chemistry scheme. These results have
been time-averaged and, since the chemical reactions are mainly confined to the lower
region of the reactor, results have been averaged over the bottom 10 centimeters of the
bed. Figures 4 and 5 also include the results of both a 2-D simulation with symmetry and
FOU with 24 z-cells. Experimental conditions and outlet concentrations of H2 predicted
by the high-order three-dimensional simulations for runs S2-S14 are summarized in Table
1.
RUN T(o C) M po (g) Ho (cm) yo (%) Uo /Um f ȳH (%) MFIX ȳH (%)
2 2
S2 606.8 1338.6 30.6 5.0 5.47 9.52 9.0
S5 609.3 1358.1 33.2 14.0 6.07 24.5 23.6
S12 596.1 2046.0 48.0 25.0 6.85 40.0 39.0
S14 598.4 1315.7 30.5 9.29 17.06 17.0 17.0

Table 1: Experimental conditions and MFIX results.

8
 0.68 0.72

Voidage 0.64 0.67

Voidage
' 0.6 ' 0.62

0.56 0.57

0.52 0.52
0 1 2 3 0 1 2 3
Radius (cm) Radius (cm)

Figure 3: Radial Voidage Profiles Averaged Over Time and the Heights 20-30 cm
and 30-34 cm.

0.035 0.018
Mass Fraction SiH4

Mass Fraction H2

0.025 0.014
) *

0.015 0.01

0.005 0.006
0 1 2 3 0 1 2 3
Radius (cm) Radius (cm)

Figure 4: Radial Mass Fraction Profiles of SiH4 and H2 .

9
 3e-07 0.0055

Mass Fraction Si2H6

Mass Fraction SiH2
0.0045

2e-07 0.0035
) )
0.0025

0.0015

5e-08 0.0005
0 1 2 3 0 1 2 3
Radius (cm) Radius (cm)

Figure 5: Radial Mass Fraction Profiles of SiH2 and Si2 H6 .

Similar high-order three-dimensional simulations were conducted using the global chem-
istry scheme. These results showed very little difference in the mass fraction of SiH4 and
H2 , as well as, outlet concentrations of H2 . Hence, these results are not shown. The fact
that very little difference was observed between the global and detailed schemes suggests
that the dominate reaction mechanism is certainly due to the heterogeneous reaction. Fi-
nally, when the effects of the chemistry (global or detailed) were included, CPU times
increased by roughly a factor of 10 with the detailed scheme being only slightly more
expensive than the global scheme.

5 Conclusion
This investigation has demonstrated that two-fluid models can be used to accurately model
silane pyrolysis in a gas-solids fluidized bed. The results showed excellent agreement
with experimental outlet concentrations of hydrogen and established that either a global
or detailed chemistry scheme can be used with similar accuracy and computational effort.
Many researchers still continue to perform two-dimensional simulations with symme-
try and/or three-dimensional FOU simulations because of the obvious reduction in CPU
times. However, this investigation has demonstrated that these techniques can predict
qualitatively different bed dynamics and species concentrations compared to those calcu-
lated using high-order three-dimensional simulations.

10
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