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INDIAN CHEMICAL ENGINEER – 2011 Indian Institute of Chemical Engineers

Vol. 53 No. 2 June 2011, pp. 6167


Print ISSN: 0019-4506, Online ISSN: 0975-007X, http://dx.doi.org/10.1080/00194506.2011.659537

Studies on Hydrochlorination of Silicon in a


Fixed Bed Reactor

M.P. Jain1*, D. Sathiyamoorthy2 & V. Govardhana Rao3


1
Food Technology Division, Bhabha Atomic Research Centre, Mumbai 400085, India
2
Powder Metallurgy Division, Bhabha Atomic Research Centre, Mumbai 400085, India
3
Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai
400076, India

Abstract: The work presented here pertains to the study of hydrochlorination of silicon in a
Section A

fixed bed reactor to produce primarily trichlorosilane. Most of the data on this reaction system is
patented. Reaction takes place between hydrogen chloride gas and dry silicon powder in a fixed
bed condition. The optimum temperature for this reaction was determined by changing the
reaction temperature and collecting the condensed product of this reaction, i.e. trichlorosilane,
and was found to be 3218C at atmospheric pressure. Using the reaction kinetics theory, fixed bed
reaction rate constants were determined for 124, 141, 160, 208 and 438 mm average silicon
particle sizes at 3218C and atmospheric pressure. It was observed that the fixed bed reaction rate
constant values were of the same order and around 0.7 s 1. The conversion of HCl increases
with a decrease in particle size of silicon and lowering of the superficial velocity of HCl gas.

Keywords: Fixed bed reactor, Silicon, Hydrochlorination, Reaction rate constant.

Introduction
Most of the data on this reaction system are patented for commercial reason. An
account of work on this reaction system in a batch reactor is presented by Pauls [1]. Li
et al. [2] produced trichlorosilane in a fluidized bed reactor and found that low flows
of 25 Umf of HCl gas are better for achieving a good yield of trichlorosilane.
However, it is well known that a fixed bed reactor gives the maximum conversion as
compared with a fluidized bed reactor, although there are various other advantages for
a fluidized bed reactor.

*Author for Correspondence. E-mail: mpjain2000@yahoo.com


62 JAIN ET AL.

An equation was derived for the estimation of the reaction rate of HCl gas for hydrochlorina-
tion of silicon. Levenspiel [3] described the method to derive this equation. Hydrochlorination of
silicon particles of 124, 141, 160, 208 and 438 mm average diameter was carried out to produce
trichlorosilane, and the conversion of HCl to trichlorosilane thus obtained was estimated. The
following equations were used to estimate reaction rate constant in a fixed bed, minimum fluidizing
velocity, Reynolds number and Archimedes number.
Reaction Rate Constant in Fixed Bed
The reaction rate constant in fixed bed reactor assuming a plug flow was determined using:
Kr H ð1  emf Þ
¼ ð1 þ eA Þ lnð1  XA Þ  eA XA (1)
U0

Minimum Fluidization Velocity


Minimum fluidization velocity was calculated utilizing Chitester et al.’s [4] equation for the particle
size range 124438 mm:
 0:5
Remf ¼ 28:72 þ ð0:0408ÞAr  28:7 (2)
dp Umf qf
Remf ¼ (3)
lg
dp3 qf ðqs  qf Þg
Ar ¼ (4)
l2g

Materials and Methods


Experiments were carried out in a laboratory reactor as shown in Fig. 1 in fixed bed mode to obtain
experimental conversions of HCl to trichlorosilane. The reaction between hydrogen chloride gas
and silicon [5] takes place as follows:
321 C
Si þ 3HCl ! SiHCl3 þH2 þ 115 kcal (5)
1:0 atm

The experimental setup, using an SS316L, consisted of a reactor with 2.665 cm i.d. and 47 cm
height. HCl gas was supplied through a perforated plate called a distributor located at the joint of
reactor and a cone at the bottom. A pressure gauge was provided at the top of the reactor. Oven-
dried silicon powder was introduced from the top to obtain an initial height of the bed of be about
10 cm. This required approximately 56 g silicon powder of 438 mm size. The product trichlorosilane
was collected in a vessel after condensation. The temperature in the reactor was obtained with the
help of a tracer coil heater and an onoff controller. The temperature of the reactor was measured
using a thermocouple located in the lower middle portion of the reactor. Insulation with glass wool
was provided for the reactor, and for heat removal during the exothermic reaction air flowed
through a copper coil brazed around the reactor. Silicon powder was supplied from a silicon bin
connected to the reactor. First the reactor was operated at different temperatures to find the optimum
temperature for production of trichlorosilane with 438 mm silicon particles. Condensed

INDIAN CHEMICAL ENGINEER Vol. 53 No. 2 June 2011


Studies on Hydrochlorination of Silicon in a Fixed Bed Reactor 63

Fig. 1. Experimental setup for trichlorosilane production.

trichlorosilane was collected in a small flask and weighed to determined the optimum temperature
for trichlorosilane production at the same HCl flow rate and the same particle size of 438 mm.
Vapours of uncondensed trichlorosilane were passed through and reacted with NaOH solution in a
flask and the contents were analysed.
Superficial gas velocity was kept lower than the minimum fluidization velocity for a particular
size (e.g. 160 mm) of silicon particle to determine the fixed bed condition rate constant. The
trichlorosilane generated was not condensed but reacted directly with caustic soda solution to
estimate the fixed bed condition reaction rate constant and conversions of HCl to trichlorosilane.
Silica formed by the reaction of trichlorosilane with NaOH was precipitated, washed, dried and
weighed to estimate the conversion of HCl to trichlorosilane. The HCl flow rate was maintained at
0.6 l min 1 for 160 mm silicon particles. Precipitated, washed and dried silica was used to back-
calculate the HCl gas used to making trichlorosilane, as per Equations (5) and (6):

SiHCl3 þ 3NaOH ! SiO2 þ 3NaCl þ H2 þ H2 O (6)

INDIAN CHEMICAL ENGINEER Vol. 53 No. 2 June 2011


64 JAIN ET AL.

The unconverted portion of HCl was also neutralized by NaOH

HCl þ NaOH ! NaCl þ H2 O (7)


The HCl conversion was estimated by determining the ratio of HCl used to make trichlorosilane and
total HCl flow as feed. Here, trichlorosilane was reacted with caustic soda to give silica. Estimation
of silica in turn gave the quantity of HCl used up. Conversion of HCl was used to estimate the
reaction rate constant from Equation (1).
The boiling point of the produced trichlorosilane was 328C and matched well with the literature
value for trichlorosilane. Specific gravity was found to be 1.37, which was slightly high compared
with the value given in the literature (1.34). A sample checked in a gas chromatograph showed
94.4% purity of trichlorosilane.

Results and Discussion


Initially the reactor was operated for the hydrochlorination of silicon in fixed-bed conditions for 438
mm (average size) particles and optimum yield of trichlorosilane was obtained at an average
temperature of 3218C. Trichlorosilane production started after 2508C, and at 3218C it was
maximum and then showed decrease in production rate for 438 mm silicon particles. This
experimental data is depicted in Fig. 2. Therefore all other fixed bed experiments were carried out at
3218C average temperature. Conversions of HCl and reaction rate constants in fixed bed conditions
were experimentally determined for various sizes of silicon particles, viz. 124, 141, 160 208 and
438 mm at 3218C, as shown in the Appendix and Fig. 3. Figure 3 shows that conversion of HCl
decreased as the silicon particle size increased owing to the reduction in total surface area available
for the reaction. Table 1 shows conversions of HCl for 208 mm silicon particles at various flow rates
and the data is depicted in Fig. 4. It shows that conversion of HCl decreased as the HCl gas flow
increased owing to the availability of reduced residence time for the gas for reaction in the reactor.

5
4.5
4
trichlorosilane, g/min.
Rate of production of

3.5
3
2.5
2
1.5
1
0.5
0
250 280 300 320 330 340
Temperature, °C

Fig. 2. Rate of production of trichlorosilane vs temperature. HCl flow rate, 2.2 l min 1; particle size, 438 mm.

INDIAN CHEMICAL ENGINEER Vol. 53 No. 2 June 2011


Studies on Hydrochlorination of Silicon in a Fixed Bed Reactor 65

Silicon bed dia.=2.665 cm, ht.=10 cm, temp.=321°C


1.00

0.95

0.90

Conversion of HCl, XA
0.85

0.80

0.75

0.70

0.65

0.60
100 150 200 250 300 350 400 450
Average dia. of silicon particles, microns

Fig. 3. Conversion of HCL vs average silicon particle diameter.

There was some variation in the values of reaction rate constant Kr, but the order was same and
values were around 0.7 s 1 for most of the particle sizes and also at different flow rates, as shown
in Table 1 and the Appendix.

Conclusion
Optimum yield of trichlorosilane was obtained at an average temperature of 3218C. Conversion of
HCl decreased with increasing HCl gas flow rate in the fixed bed condition. Total surface area per
unit volume of the bed also decreased with increase in the size of silicon particles. Therefore
conversion of HCl decreased with increasing silicon particle size. The reaction rate constant for
hydrochlorination of silicon in fixed bed condition was approximately 0.7 s 1.

Table 1. Experimental data for hydrochlorination of 208 mm silicon particles

Sample no. Description 208 mm Si particle bed

1 HCl gas flow, l min 1 1.0 0.7 0.4 0.2


2 Superficial gas velocity cm s 1 2.99 2.09 1.195 0.6
3 Reaction time for production of trichlorosilane, min 10 8 20 5
4 Total HCl gas fed, g 16.295 9.125 12.984 1.623
5 Dry silica produced, g 6.914 4.388 7.051 0.885
6 HCl gas used stoichiometrically, g 12.618 8.01 12.868 1.615
7 Reaction rate constant for fixed bed, s 1 0.74 0.674 0.779 0.66
8 Conversion of HCl gas 0.77 0.88 0.991 0.995

Fixed bed height,10 cm; average temperature of reaction, 3218C.

INDIAN CHEMICAL ENGINEER Vol. 53 No. 2 June 2011


66 JAIN ET AL.

L/D=3.752, 321°C, average silicon particle size 208 microns


1.00

0.95

Conversion of HCl, XA
0.90

0.85

0.80

0.75
0.5 1.0 1.5 2.0 2.5 3.0
Superficial gas velocity, cm/s

Fig. 4. Conversion of HCl vs superficial gas velocity.

Nomenclature
Ar Archimedes number
dp particle diameter, m
D internal diameter of the reactor, m
g gravitational acceleration, m s 2
H height of bed above distributor, m
Kr fixed bed reaction rate constant, m3 m 3 catalyst s 1
L height of the packed bed, m
Remf Reynolds number at minimum fluidization velocity
Uo superficial velocity of fluidizing gas, m s 1
Umf superficial gas velocity at incipient fluidization, m s 1
XA conversion of HCl
rs density of solid particle, kg m 3
rf density of the reactant gas, kg m 3
oA volume ratio of product gases to input gases
omf fraction of bed at incipient fluidization
mg viscosity of the reactant gas, kg/m.s

Acknowledgements
The authors thank Dr A.K. Sharma, Head, Food Technology Division, BARC, Mumbai, for
supporting this work.

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Studies on Hydrochlorination of Silicon in a Fixed Bed Reactor 67

References
1. Pauls, G., ‘‘Production of Trichlorosilane’’, US Patent 2,943918, 5 July (1960).
2. Li, K.Y., Peng, S.H. and Ho, T.C., Fluidization Engineering Fundamentals and Applications, AIChE
Symposium Series no. 262, Vol. 84, pp. 115125 (1988).
3. Levenspiel, O., Chemical Reaction Engineering, 3rd edn, John Wiley and Sons, New York, p. 395 (1999).
4. Chitester, D.C., Kornosky, R.M., Fan, L. and Danko, J.P., ‘‘Characteristics of Fluidization at High
Pressure’’, Chem. Eng. Sci., 39, pp. 253261 (1984).
5. Jain, M.P., Sathiyamoorthy, D. and Rao, V. Govardhana, ‘‘Studies on Hydrochlorination of Silicon in a
Fluidized Bed Reactor’’, Indian Chem. Engr, 51(4), 272280 (2009).

Appendix
Table A1. Fixed bed condition estimation of conversion of HCl and reaction rate constant for 124438 mm
silicon particles

Particle size, mm

Sample no. 124 141 160 208 438

1 HCl gas flow, l min 1 0.3 0.2 0.6 0.7 1.75


2 Reaction time for trichlorosilane production, min 14 15 8 8 6.5
3 Total HCl gas fed, g 6.8438 4.869 7.821 9.125 18.535
4 Dry silica produced, g 3.746 2.633 3.956 4.388 6.574
5 HCl gas used stoichiometrically, g 6.837 4.805 7.22 8.01 11.996
6 Reaction rate constant for fixed bed, s 1 0.693 0.6 0.723 0.674 0.767
7 Conversion of HCl gas 0.995 0.987 0.923 0.88 0.6472

Fixed bed height, 10 cm; average temperature of reaction, 3218C.

INDIAN CHEMICAL ENGINEER Vol. 53 No. 2 June 2011


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