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Chemical Engineering Science 65 (2010) 499 -- 503
A R T I C L E I N F O A B S T R A C T
Article history: The reaction characteristics of two-step oxychlorination to produce 1,2-dichloroethane as a feedstock of
Received 7 July 2008 PVC production were determined in a fluidized bed reactor. The effects of superficial gas velocity and
Received in revised form 12 February 2009 gas composition on the reactivity and fluidization stability have been determined to find the optimum
Accepted 24 February 2009
operating conditions in the continuous fluidized bed reactor system. It has been found that the average
Available online 1 April 2009
ethylene conversion is 94% with ethylene dichloride (EDC) selectivity of 9798%, the average HCl conver-
Keywords:
sion is 97.4%, the solid reactant conversion is 54% and a solid inventory ratio for the optimum reaction
Two-step oxychlorination conversion is 3.3 in the process.
1,2-Dichloroethane 2009 Elsevier Ltd. All rights reserved.
Fluidized bed reactor
Solid inventory ratio
Continuous process
0009-2509/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2009.02.052
500 K.S. Go et al. / Chemical Engineering Science 65 (2010) 499 -- 503
reactor system has smooth liquid-like flow of particles which allows occurs with channeling (Compo and Preffer, 1987).
continuous solid circulation operation with rapid mixing of solids
(Kunii and Levenspiel, 1991). The solid inventory ratio for the reduc- Q = P/ P0 (4)
tion and oxidation reactions is an important factor to maintain the
where P0 is the pressure drop by the bed weight and P is pressure
mass balance in the continuous fluidized bed reaction system.
drop at any time.
In this study, the two-step oxychlorination reaction for EDC pro-
The catalyst of 170 g (bed length/column diameter = 3) was
duction was carried out in a batch fluidized bed reactor. First of all,
packed in the reactor and fully oxidized before reaction. After the
the fluidization stability was determined based on the variation of
reaction, the sample of catalysts was observed by optical microscope
bed pressure drop during the reaction. The optimum gas velocity
(EgTech, Korea).
and the feeding compositions were determined at 523 K. With these
optimized values, solid reactant conversion and solid inventory ratio
3. Results and discussion
were determined for the continuous fluidized bed process.
3.1. Fluidization stability in two-step oxychlorination reaction
Cyclone
Freeboard
C 2H 4 MFC
N2 MFC
P/T6 (15cm)
O2 MFC P/T5 (12cm)
HCI MFC P/T4 (9cm) Heating
P/T3 (6cm) coil
P/T2 (3cm) pH-
P/T1 (1cm) 3-way meter
valve
Distributor
Air
Gas
box Pre-
Chromatography
heater
Fig. 1. Schematic diagram of the fluidized bed reactor for oxychlorination reaction (P/T: pressure tap).
K.S. Go et al. / Chemical Engineering Science 65 (2010) 499 -- 503 501
increase of bubble size and bubble formation frequency in the bed of reaction time is shown in Fig. 6 where the reactivity of reduction
larger particle size. Also, Pan et al. (1994) reported that deactivation depends on ethylene feeding concentration and the reaction rate ap-
of the catalyst can be prevented at the O2 /HCl ratio in the range of proaches to its maximum value above 50% concentration of ethylene
0.30.75 in the oxidation stage so that it may be claimed that the and the EDC selectivity is mainly dependent on the ethylene conver-
O2 /HCl molar ratio of 0.5 is a desirable one for the reaction. sion. The average EDC selectivity is found to be 9798% in the ethy-
lene conversion range above 90% while it decreases with increasing
3.2. Effects of gas velocity and ethylene concentration on the reduction unreacted ethylene. With the constant supply of ethylene in the re-
reaction actor, the amount of CuCl2 to participating in the reaction becomes
smaller which may cause unreacted ethylene in the reactor. For this
After oxidizing the fresh catalyst completely, the reduction re- reason, decreasing EDC selectivity can be interpreted by increase of
action was carried out. At an ethylene feeding concentration below the byproducts from the side-reaction between the unreacted ethy-
the stoichiometric value, the effect of gas velocity (0.0040.024 m/s) lene and EDC.
in terms of gas residence time in the bed on the ethylene conver-
sion and EDC selectivity in the reduction reaction was determined 3.3. Effect of gas velocity and hydrogen chloride concentration on the
as shown in Fig. 5. As can be seen, the ethylene conversion increases oxidation reaction
with increasing gas residence time or decreasing gas velocity in the
bed since bubble size is smaller at the lower gas velocities that may After the reduction reaction, the oxidation reaction was carried
improve the contacting area between the gas and solid phases. How- out at a O2 /HCl molar ratio of 0.5. At a hydrogen chloride feeding
ever, the effect of gas residence time of ethylene is insignificant to concentration below the stoichiometric value, the effect of gas ve-
the EDC selectivity at approximately 98% that is acceptable range in locity (0.0030.012 m/s) in terms of gas residence time in the reactor
the present reaction system. on hydrogen chloride conversion was determined as shown in Fig. 7.
At a gas residence time of 10 s, the effect of ethylene feeding con-
centration on the ethylene conversion and EDC selectivity with the
16
1.4
1.4
Standard deviation of the bed pressure drop [Pa]
1.2 14
Q [-]
1.0
0.8 12
1.2 0.6 without inert gas
Fluidization stability, Q [-]
0 10 20 30 40 50 10
Reaction time [min]
1.0
8
stoichiometric
6 ratio point
0.8
0.0 0
0 10 20 30 40 50 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Reaction Time [min] O2 / HCl molar ratio [-]
Fig. 2. Fluidization stability of the oxidation and the reduction reactions. Fig. 4. Effect of O2 /HCl molar ratio on fluidization stability.
Fig. 3. Optical microscope images of the reactant particles (a) before and (b) after oxidation.
502 K.S. Go et al. / Chemical Engineering Science 65 (2010) 499 -- 503
95
90
95
90
C2H4 conversion [%]
75 60
85
C2H4 conversion
70 EDC selectivity 50
0 0
0 5 10 15 20 25 30 35 80
Gas residence time, V / F [s]
0
Fig. 5. Effect of gas residence time on ethylene conversion and EDC selectivity. 0 10 20 30 40
Gas residence time, V / F [s]
80 CC2H4 = 7 % 100
CC2H4 = 15 %
60 CC2H4 = 30 %
CC2H4 = 50 %
40 CC2H4 = 75 % 95
20
HCl conversion [%]
0
100 90
80
EDC selectivity [%]
60 85
CHCl = 20 %
40 CHCl = 30 %
CHCl = 40 %
20 CHCl = 50 %
80
0
0 10 20 30 40 50 60 70 0
Time [min] 0 10 20 30 40 50 60
Time [min]
Fig. 6. Effect of ethylene concentration on ethylene conversion and EDC selectivity.
Fig. 8. Effect of hydrogen chloride concentration on its conversion.
As can be seen, the hydrogen chloride conversion increases approxi- 3.4. Solid inventory ratio of the two-step oxychlorination for the
mately 95% conversion over 20 s with increasing gas residence time. continuous system
Comparing with the reduction data, contacting time between the
gas and solids in the oxidation reaction is twice longer. Therefore, Based on the obtained data, the solid inventory ratio was de-
the oxidation reaction rate is relatively slow than that of the reduc- termined for the continuous two-step oxychlorination process. The
tion reaction. The effect of hydrogen chloride concentration on its solid inventory ratio is defined as the ratio of solid mass weight
conversion at a gas residence time of 20 s is shown in Fig. 8. The (Wox /Wred ) needed for maintaining the mass balance of oxidation
maximum conversion of hydrogen chloride is found to be 9798% and reduction for the continuous process and this is a function of
regardless of the feeding concentration but the reaction rate in- solid residence time in the reaction. Based on the average ethylene
creases with increasing feeding concentration at the given reaction conversion of 94% (Rred,gas = 10 s, CC2 H4 = 50%) with EDC selectivity
condition. of 9798% and the average hydrogen chloride conversion of 97.4%
K.S. Go et al. / Chemical Engineering Science 65 (2010) 499 -- 503 503
(Rox,gas = 20 s, CHCl = 50% at O2 HCl = 0.5) from Figs. 6 and 8, the solid Hr0 enthalpy of reaction, kJ/mol
inventory ratio can be determined to be 3.3. It can be also interpreted Mr mole of copper reacted, mol
by the solid reactant conversion defined by Mtr mole of copper to react, mol
P pressure drop, Pa
Xs = Mr /Mtr (5) P0 the pressure drop by bed weight, Pa
Q fluidization stability
where Xs is solid reactant conversion, Mr mole of copper reacted,
Rox,gas gas residence time in oxidation, s
and Mtr mole of copper to react. As a result, solid reactant conversion
Rred,gas gas residence time in reduction, s
is found to be 54% at the optimum operating condition. Although
Umf minimum fluidizing gas velocity, m/s
Wachi and Asai (1994) reported in their kinetic study of the reduc-
V volume of solid particle in the bed, m3
tion that the solid conversion of 64% was obtained at the optimum
Wox solid mass weight in oxidation, kg
performance, this difference from this study is a reasonable one since
Wred solid mass weight in reduction, kg
contacting efficiency between gas and solid phases in the fluidized
Xs conversion of solid reactant, %
bed reactor is relatively lower than in an ideal reactor for the kinetic
study. Meanwhile, there was no observation of catalyst sublimation
Acknowledgment
due to the heat of reaction and the particle attrition during the flu-
idization operation was insignificant for the reaction.
This work was supported by the Brain Korea 21 project from the
In view of designing the present process, two interconnecting
Ministry of Education, Science and Technology.
bubbling fluidized bed reactors with the solid inventory ratio of 3.3
can be selected as a continuous two-step oxychlorination system
References
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Notation