Kinetic of Allylation of Phenol Using Quaternary Ammonium Membrane in Membrane Reactor

Ho-Shing Wu*, Chang-Lin Lee and Yu-Kai Wu

Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan, 32003, Taiwan.

Abstract
Lab-produced anion exchange membranes (TMA and TBA) were prepared by polymerizing chloromethylstyrene with cross-linked reagent of divinylbenzene
with a coating on polypropylene non-woven fabric using the paste method, and then immobilized with trimethyl and tributyl amine in the quaternarization

P-1 process. The properties of these membranes were characterized in terms of ion-exchange capacity and SEM image. The kinetics of allylation of phenol was
investigated in the organic and alkali aqueous solution in a vertical membrane reactor. The operating conditions, such as reaction temperature, kind of
membrane (two lab-produced and one commercial membranes), and concentration ratio of reactants were conducted to achieve the optimum condition. The
reactivity of allylation of phenol using lab-produced membrane was larger than that using commercial A172 membrane.

Preparation of Anion Exchange Membrane

70 20
H2C CH HC CH2 H2C CH CH CH2
60
50 18
40
16
30
C Cl -
20 14

Yield of PhOR (%)

+ ClH2C
H2C CH R N R H2C CH
R n n 10 c
0
12
base membrane anion exchange membrane
30 10
Yield of PhOR (%)
The base membrane was made from 25 8
chloromethylstyrene, divinylstyrene and PP 20
6
(polypropylene) non-woven fabric. 15
10 4
The cross-linked degree (%) = 5 b 2
divinylbenzene (mol)/(vinylbenzyl chloride (mol) + 0
divinylbenzene (mol))×100. 0
10
0 50 100 150 200 250
Kinetics of membrane-based permeation 8
Time (min)
stirred cell 6

4
Yield of PhOR for different degrees of corsslinkage
6 (○: CL = 4 mol%, ▽: CL = 6 mol%, □: CL = 8 mol%,
2 a ◇: CL = 10 mol%, △: CL = 15 mol%) of TMA
8mm 0 45℃, 400rpm, aqueous phase 55cm3
0 50 100 150 200 250
7 0.004 mol of PhONa , phenol ： NaOH=1:1.67
Time (min)
organic phase: C2H4Cl2, 55 cm3, 0.004 mol of C3H5Br
13mm Plot of yield of PhOR vs reaction time for various
30mm
membranes (a) phenol: allyl bromide = 1:1
3 40mm
4
(b) phenol: allyl bromide = 3:1
13mm (c)phenol: allyl bromide = 1:15
30mm
12mm ○: TMA, ▽: TBA, □: A172, ◇: base membrane
Schematic diagram of vertical membrane62mm reactor.
1: membrane, 2 teflon stir bar, 1
3: stainless stirrer, 4:membrane reactor,
38mm
40mm 60 100
20mm
5 magnetic stirrer, 6: mechanical stirrer,
2
7: sampling point, 8: cooling circulator bath, 50
80
Cl percentage in membrane (%)

9 organic phase, 810: aqueous phase. 5

Yield of PhOR (%)

40
60
The mechanism in a two phases x3.14x1.2=55membrane
(3.8/2) x3.14x(4-1.2)+((6.2+3.8)/4) 2 2
30

system 40
20
-

20
10

0 0
0 50 100 150 200 250

Time (min)

Chloride density in the membrane and plot of yield of PhOR SEM image of surface for different membrane.
vs reaction time for (a)Non-woven PP fabric
45℃, 400rpm, aqueous phase 55cm3 (b)(b) base membrane
0.004 mol of PhONa, phenol: NaOH=1:1.67 (c) TMA (CL=4mol%, 24 h 50oC)
organic phase: C2H4Cl2, 55 cm3, 0.032 mol of C3H5Br (d) TMA (CL=15mol%, 24 h 50oC)
Results ○: data from different run, ▽: data form same run.
3.0
a 1.8 60
2.8 ACKNOWLEDGMENT
1.6
2.6 50
1.4 We would like to thank the National Science Council of the
2.4
Ion exchange capacity (mmol/g)

Republic of China for financial support of this research

r (mol/(m2.min))*1000

1.2 40
Yield of PhOR(%)

2.2
under grant No NSC 91-2214-E155-006.
1.0
2.0
30
2 4 6 8 10 12 14 16
0.8
1.5
b
1.2 0.6 20
R

0.9 0.4
10
0.6 0.2

0.3 0.0 0
0 2 4 6 8 10
0.0
2 4 6 8 10 12 14 16 Molar ratio of RX/Phenol

Degree of crosslinkage (mol%) Dependence of the reaction rate per area on the molar ratio of
RX/phenol.
Ion exchange capacity of (a) TMA and (b) TBA at different
imobilized time and temperature.
0.1 kmol/m3 of tertiary amine in meethyl alcohol solution
450rpm. 30oC: ○ 24h, ⊙48h, ▽ 72h ; 40oC: △ 72h.