Electronic Supplementary Material (ESI) for Reaction Chemistry & Engineering. This journal is © The Royal Society of Chemistry 2016
Catalytic distillation for ethyl acetate synthesis using microfibrous-structured
Nafion-SiO2/SS-fiber solid acid packings
Tao Deng, Yakun Li, Guofeng Zhao, Zhiqiang Zhang, Ye Liu and Yong Lu* Table S1. Effects of coating composition on acidity and durability of the structured catalyst. 1 h ultrasonic 2 h ultrasonic 3 h ultrasonic 4 h ultrasonic 5 h ultrasonic Coating Total loading IEC concussion concussion concussion concussion concussion compositiona (wt%) (mmol g-1)b (mmol g-1) (mmol g-1) (mmol g-1) (mmol g-1) (mmol g-1)
Nafion 10.7 0.09 0.01 0 0 0 0
Nafion/SiO2 17.5 0.07 0.03 0.01 0 0 0
Nafion/TEOS 25.3 0.07 0.07 0.07 0.07 0.07 0.07 a. The coating solution were 5 wt% Nafion polymer dispersion, SiO2 sol-gel in 5 wt% Nafion polymer dispersion and TEOS in Nafion polymer dispersion with the same Nafion:additives weight ratio of 2:1. b. The ion-exchange capacity (IEC) was used to represent the catalyst acid capacity. 100 190℃
% 200℃ t
w 210℃
/ 90 220℃ e t
a 230℃ t e c a
l
y 80 h t e
f o
y t
i 70 r u p
e h
T A 60 0 2 4 6 8 Time / h
20 190℃
% 200℃ t
w 210℃
/ 15 ℃
e 220 t
a 230℃ t e c a
l
y 10 h t e
f o
y t
i 5 r u p
e h
T B 0 0 2 4 6 8 Time / h
Figure S1. Effect of reboiler temperature (duty) on the purity of ethyl acetate at the top
(A) and bottom (B) of the column for every 1 hour. Reaction conditions: molar feed
ratio of acetic acid to ethanol = 1:1, reflux ratio = 2.5, WHSV = 0.3 h-1, molar ratio of acetic acid to ethanol in the flask = 1.2:1, catalyst amount = 8.5 mmol H+. 100 % t w
/
e 90 t a t e c a
l y h
t 80
e 1:1
f
o 1.2:1
y 1.5:1 t i
r 1.8:1 u
p 70 2:1
e h
T A 0 2 4 6 8 Time / h
15 % t w
1:1 /
e 1.2:1 t
a 10 t 1.5:1 e
c 1.8:1 a
2:1 l y h t e
f
o 5
y t i r u p
e h
T B 0 0 2 4 6 8 Time / h
Figure S2. Effect of molar ratio of acetic acid to ethanol on the purity of ethyl acetate at the top (A) and bottom (B) of the column for every 1 hour. Reaction conditions: reboiler temperature = 220 oC, reflux ratio = 2.5, WHSV = 0.3 h-1, molar ratio of acetic acid to ethanol in the flask = 1.2:1, catalyst amount = 8.5 mmol H+. 100 % t w
/
e 90 t a t e c a
l y h t 80 -1 e
WHSV = 0.3h f -1 o
WHSV = 0.4h
y -1 t
i WHSV = 0.5h r -1 u WHSV = 0.6h
p 70 -1
e WHSV = 0.7h h
T A 0 2 4 6 8 Time / h
WHSV = 0.3h-1 25 -1
% WHSV = 0.4h t -1
w WHSV = 0.5h
/ 20 -1 e WHSV = 0.6h t -1 a
t WHSV = 0.7h e c
a 15
l y h t e
f 10 o
y t i r
u 5 p
e h
T B 0 0 2 4 6 8 Time / h
Figure S3. Effect of WHSV on the purity of ethyl acetate at the top (A) and bottom (B) of the column for every 1 hour. Reaction conditions: reboiler temperature = 220 oC, reflux ratio = 2.5, molar feed ratio of acetic acid to ethanol = 1.2:1, molar ratio of acetic acid to ethanol in the flask = 1.2:1, catalyst amount = 8.5 mmol H+. 100 % t w
/
e t a t e
c 90 a
l y h t e
reflux ratio = 1 f
o reflux ratio = 2
y
t reflux ratio = 2.5 i r 80 reflux ratio = 3 u
p reflux ratio = 4
e
h A T 0 2 4 6 8 Time / h
% 25 reflux ratio = 1 t
w reflux ratio = 2
/ reflux ratio = 2.5 e t reflux ratio = 3 a 20 t
e reflux ratio = 4 c a
l
y 15 h t e
f o
y 10 t i r u p
e 5 h B T 0 2 4 6 8 Time / h
Figure S4. Effect of reflux ratio on the purity of ethyl acetate at the top (A) and bottom
(B) of the column for every 1 hour. Reaction conditions: reboiler temperature = 220 oC, molar feed ratio of acetic acid to ethanol = 1.2:1, WHSV = 0.5 h-1, molar ratio of acetic acid to ethanol in the flask = 1.2:1, catalyst amount = 10.5 mmol H+. 100 % t w
/ 90 e t a t e c a
l 80 y + h
t 4.5 mmol H
e +
f 6.5 mmol H
o + 8.5 mmol H y 70 t + i
r 10.5 mmol H
u +
p 12.5 mmol H
e
h A
T 60 0 2 4 6 8 Time / h
30 4.5 mmol H+ +
% 6.5 mmol H t +
w 8.5 mmol H
/ + 10.5 mmol H e
t + a 12.5 mmol H t 20 e c a
l y h t e
f
o 10
y t i r u p
e
h B T 0 0 2 4 6 8 Time / h
Figure S5. Effect of amount of the catalyst on the purity of ethyl acetate at the top (A)
and bottom (B) of the column for every 1 hour. Reaction conditions: reboiler temperature = 220 oC, reflux ratio = 2.5, WHSV = 0.5 h-1, molar feed ratio of acetic acid to ethanol = 1.2:1, molar ratio of acetic acid to ethanol in the flask = 1.2:1. 100 % t w
/
e t a t
e 90 c a
l y h t
e 1:1.5
f 1:1.2 o
y 1:1 t i r 80 1.2:1 u p
1.5:1 e
h A T 0 2 4 6 8 Time / h
25 1:1.5 %
t 1:1.2 w
20 1:1 /
e 1.2:1 t a
t 1.5:1 e 15 c a
l y h t
e 10
f o
y t i r 5 u p
e h
T B 0 0 2 4 6 8 Time / h
Figure S6. Effect of molar ratio of acetic acid to ethanol in the flask on the purity of ethyl acetate at the top (A) and bottom (B) of the column for every 1 hour. Reaction conditions: reboiler temperature = 220 oC, molar feed ratio of acetic acid to ethanol =
1.2:1, reflux ratio = 2, WHSV = 0.5 h-1, catalyst amount = 10.5 mmol H+. 100 % t w
/
e t
a 90 t e c a
l y h t Run 1st e
f Run 2nd
o 80 Run 3rd y t i
r Run 4th
u Run 5th p
e
h A T 70 0 2 4 6 8 Time / h %
t 6 w
/
e t a t e
c 4 a
l y h t e
f o 2 Run 1st y t
i Run 2nd r
u Run 3rd p Run 4th e
h Run 5th B T 0 0 2 4 6 8 Time / h
Figure S7. The stability test with structured catalyst on the purity of ethyl acetate at the top (A) and bottom (B) of the column for every 1 hour in five consecutive batch experiments. Reaction conditions: reboiler temperature = 220 oC, molar feed ratio of acetic acid to ethanol = 1.2:1, reflux ratio = 2, WHSV = 0.5 h-1, catalyst amount = 10.5 mmol H+, molar ratio of acetic acid to ethanol in the flask = 1:1.2.