157

Tp ch Ha hc, T. 43 (2), Tr. 157 - 161, 2005

NGHIN CU PHN NG ANKYL HA BENZEN BNG
ETANOL TRN XC TC ZEOLIT Y BIN TNH
n Ta son 2-3-2004
Ng Th Thun
1
, Cao Hi Thng
2
1
Khoa Ha hc, Tr!ng i hc Khoa hc T nhin - i hc Quc gia H* Ni
2
Khoa Ha-L k thut, Hc vin K thut Qun s

Summary
This paper presents the benzene alkylation with ethanol catalysed on the Y and ZSM-5 zeolite.
The experimental results have shown that 30%H-ZSM-5/HY sample is the best for forming
ethylbenzene. On this sample the reaction has been carried out by central composite orthogone
design at the second level for three factors reaction temperature, flow speed and the molar ratio
of ethanol/benzene. The target function for the productivity of ethylbenzene has been yielded. By
checking the experimental and mathematic results we observed that current equation is suitable.

I - t vn
Trong vi thp k gn y, vai tr ca cht
xc tc !c khng nh trong cng nghip
lc - ha du, c bit l xc tc zeolit c rt
nhiu c tnh !u vit hn so vi cc loi xc
tc khc bi hot xc tc, n nh v
chn lc cao v nht l gii quyt !c cc p
lc v mi tr!ng. Ankyl ha l mt trong
nhng phn ng !c s dng xc tc axit, cc
xc tc truyn thng !c thay th bi xc
tc axit rn zeolit. Hin nay, h!ng nghin cu
ch yu ca phn ng ankyl ha l to ra
cumen, etylantraquinon, etylbenzen... trong
etylbenzen l ngun nguyn liu ch yu
iu ch styren cng nghip. V vy, vi mc
ch iu ch etylbenzen chng ti tin hnh
phn ng ankyl ha benzen bng etanol trn xc
tc zeolit Y v ZSM-5 ng thi s dng
ph!ng php qui hoch ha thc nghim tm
iu kin ti !u cho qu trnh to thnh
etylbenzen.
II - thc nghim
1. Chun b xc tc
Zeolit Y !c s dng l zeolit ca tr!ng
HBK t l SiO
2
/A1
2
O
3
= 2,8 v zeolit ZSM-5
c t l Si/A1 = 39 !c chuyn v dng H-Y v
H-ZSM-5 bng cch trao i vi dung dch
NH
4
NO
3
ri em nung nhit 500 - 600
o
C.
Mu xc tc HY !c bin tnh bng cch !a
thm zeolit H-ZSM-5 theo cc hm l!ng tnh
ton tr!c bng cch trn c hc trn my lc
trong vng 5 gi, sau em nung v p vin
theo kch c ht nh sn.
2. Phn ng ankyl ha benzen bng etanol
Phn ng !c thc hin trong pha kh theo
ph!ng php dng trong l ng d!i p sut
th!ng. Ly xc tc vi c ht nh sn (1 ml)
ri np vo ng thch anh, pha trn l lp thch
anh c kch th!c c ht ln hn. Thch anh
tr!c khi s dng !c un vi axit, ra sch ri
sy kh. Nhit ca h phn ng !c xc
nh bi pin nhit in Cromen-Alumen gn vi
b hin s in t c rle t ngt.
Xc tc tr!c khi tin hnh phn ng !c
hot ha nhit 500 - 600
o
C c dng khng
kh i qua trong vng 4 gi v sau cho dng
kh tr N
2
i qua.
158
Cht phn ng pha theo t l nh sn ri
!c !a vo l vi tc dng khc nhau. Khi
cht phn ng i vo ng phn ng, qua lp
thch anh pha trn hp th nhit chuyn sang
th hi; hi cht tip tc i vo vng xc tc v
ti y xy ra qu trnh chuyn ha. Sn phm
ca phn ng !c ng!ng t li dng lng qua
sinh hn ri em i phn tch trn my sc k
kh Shimadzu GC-14B vi ct tch DB-1, kh
mang nit p sut 160 kPa.
3. Xc nh axit ca xc tc
Dng ph!ng php hp ph v gii hp NH
3
theo ch!ng trnh nhit (NH
3
-TPD) xc
nh lc v l!ng cc tm axit trn xc tc. Cc
mu xc tc sau khi hp ph cn bng NH
3
d!i
iu kin xc nh s !c gia nhit theo
ch!ng trnh nhit . Khi nng l!ng nhit
cung cp ln hn nng l!ng hp ph cc phn
t NH
3
s gii hp khi b mt xc tc v !c
kh mang !a qua etector xc nh nh
l!ng.
III - Kt qu v) tho lun
1. c tnh ca xc tc
Trn c s trn, chng ti iu ch !c
cc mu xc tc t!ng ng vi 10, 20, 30,
40%H-ZSM-5/HY ng thi tin hnh phn ng
trn cc mu xc tc ny. Kt qu !c trnh
by bng 1. T bng 1 cho thy, mu xc tc
30%H-ZSM-5/HY l !u vit nht v chuyn
ha benzen, chn lc sn phm etylbenzen
kh cao. Thc hin o tnh axit ca cc mu xc
tc, kt qu thu !c trong bng 2.
Bng 1: nh h!ng ca hm l!ng zeolit H-ZSM-5 trn HY khi
t l mol etanol/benzen = 1 : 1, nhit 400
o
C, tc th tch 3 h
-1
Mu xc tc
chuyn ha
benzen, %
chn lc
etylbenzen, %
Hiu sut etylbenzen,
%
HY 34,32 37,01 12,70
10%H-ZSM-5/HY 75,81 35,89 27,21
20%H-ZSM-5/HY 82,87 47,41 39,29
30%H-ZSM-5/HY 83,12 55,24 45,92
40%H-ZSM-5/HY 84,34 52,94 44,65
H-ZSM-5 65,48 46,27 30,29
Bng 2: axit ca cc mu xc tc
STT Mu xc tc
axit, mol
NH
3
/g
xt

1 HY 156
2 30%H-ZSM-5/HY 391
3 H-ZSM-5 820
T kt qu trn thy rng axit ca cc
mu xc tc !c sp xp theo th t HY <
30%H-ZSM-5/HY < H-ZSM-5.
2. Ph'ng php qui hoch ha thc nghim
[1] v2 kt qu th nghim
Trn mu xc tc 30%H-ZSM-5/HY chng
ti tin hnh qui hoch ha thc nghim bc hai
tm trc giao vi 3 yu t nh h!ng l: tc
dng, t l mol etanol/benzen v nhit phn
ng cho hm mc tiu l hiu sut to thnh sn
phm etylbenzen.
Trong m hnh ha thc nghim bc hai tm
trc giao vi ba yu t nh h!ng hm mc tiu
!c m t bng a thc:
y = b
0
x
0
+ b
1
x
1
+ b
2
x
2
+ b
3
x
3
+ b
12
x
1
x
2
+ b
13
x
1
x
3
+
b
23
x
2
x
3
+ b
11
x
2
1
- ) + b
22
(x
2
2
- ) + b
33
(x
3
2
- )
Ph!ng trnh hm mc tiu nhm m t nh
h!ng ca tt c cc yu t ln mt qu trnh
bng mt ph!ng trnh. Chng ta s tnh !c
gi tr ca hm mc tiu tc l tnh !c kt qu
nghin cu m khng cn tin hnh th nghim.
Trong = 0,73 l h s hiu chnh, d =
159
1,215 l khong cch t tm n im sao i
vi loi m hnh ny; b
i
, b
ii
, b
ij
l cc h s hi
qui.
M ha cc yu t: x
1
l tc dng, x
2
l t
l mol etanol/benzen, x
3
l nhit phn ng, x
0
l mc gc.
Trong qu trnh tin hnh thc nghim
thc hin theo cc mc bng 3.
T cc mc thc nghim trn tin hnh 17
th nghim theo cc iu kin khc nhau trn
mu xc tc 30%H-ZSM-5/HY (th nghim
tm !c tin hnh 3 ln tnh sai s v coi
l sai s th nghim). Kt qu !c trnh by
trong bng 4.

Bng 3: Cc mc tin hnh thc nghim
Cc mc th nghim x
1
x
2
x
3
Mc gc 3 1 400
Khong bin thin 1,5 0,5 50
Mc cao (+) 4,5 1,5 450
Mc thp (-) 1,5 0,5 350
+d 4,82 1,61 461
-d 1,18 0,39 339
Bng 4: Kt qu th nghim
STT
Tc
dng, h
-1
T l mol
etanol/benzen
Nhit
phn ng,
o
C
chuyn
ha benzen,
%
chn lc
sn phm
etylbenzen, %
Hiu sut sn
phm
etylbenzen, %
1 1,5 0,5 350 74,64 41,24 30,78
2 4,5 0,5 350 96,81 54,89 53,14
3 1,5 1,5 350 87,71 32,14 28,19
4 4,5 1,5 350 73,90 40,73 30,10
5 1,5 0,5 450 60,60 57,00 34,54
6 4,5 0,5 450 65,31 53,86 35,18
7 1,5 1,5 450 85,17 48,20 41,05
8 4,5 1,5 450 75,31 54,23 40,84
9 4,82 1,0 400 69,52 52,67 36,17
10 1,18 1,0 400 96,31 44,59 42,94
11 3,0 1,61 400 91,21 28,19 25,71
12 3,0 0,39 400 95,03 50,26 47,76
13 3,0 1,0 461 91,45 46,37 42,41
14 3,0 1,0 339 87,22 40,32 35,17
15 3,0 1,0 400 83,12 55,24 45,92
16 3,0 1,0 400 82,19 56,72 46,62
17 3,0 1,0 400 82,56 54,77 45,22
160
T cc gi tr thc nghim v tm !c tnh
h s hi qui b
i
, b
ii
, b
ij
t!ng ng. So snh vi
gi tr t
tnh
thu !c trn vi gi tr t
bng
(95%,
2) = 4,03 v loi b nhng h s hi qui khng
c ngha (c gi tr t < t
bng
) thu !c ph!ng
trnh hi qui cho hiu sut to thnh etylbenzen
nh! sau:
y = 37,99 + 1,50x
1
- 3,68x
2
+ 1,66x
3
- 2,66x
12
-
2,98x
13
+ 4,73x
23
- 3,19x
2
2
- 1,80x
3
2
(1)
Tnh ton gi tr l thuyt theo ph!ng trnh
hi qui trn ri so snh vi gi tr thc nghim
nh gi tnh ph hp ca ph!ng trnh hi
qui theo chun Fisher: F
tnh
= 17,65 < F
bng
(95%,
9, 2) = 19,33.
Nh! vy, s sai khc gia gi tr l thuyt v
gi tr thc nghim l khng ng k tc l
ph!ng trnh hi qui thu !c trn l thch
ng. Trn c s hm mc tiu tm !c, tm
iu kin ti !u bng ph!ng php ly o hm
ring theo tng yu t:
0x
1
+ 2,66x
2
+ 2,98x
3
= 1,50
-2,66x
1
- 6,38x
2
+ 4,73x
3
= 3,68
-2,98x
1
+ 4,73x
2
- 3,60x
3
= -1,66
Gii h ph!ng trnh v qui v gi tr thc
chng ti thu !c iu kin ti !u cho qu
trnh l:
x
1
= - 0,226 tc dng l 2,66h
-1

x
2
= - 0,066 t l mol etanol/benzen l 0,97
x
3
= 0,562 nhit phn ng l 428
o
C
Tin hnh phn ng ti iu kin ti !u va
tm !c th hiu sut etylbenzen l 53,87% so
vi kt qu tnh theo ph!ng trnh hi qui l
54,02%. S sai khc ny l nm trong khong
sai s th nghim nn ph!ng trnh thu !c
trn l ph hp.
Tho lun
Nh! vy, hiu sut to thnh sn phm
etylbenzen ca phn ng ankyl ha benzen bng
etanol trn xc tc 30%H-ZSM-5/HY theo
ph!ng trnh hi qui (1) v thy rng:
- C 3 yu t tc dng, t l mol
etanol/benzen v nhit phn ng u nh
h!ng n qu trnh phn ng.
- Cc yu t nh h!ng kh phc tp, khng
nhng khng tc ng c lp m cn c mi
lin h ng thi vi nhau nh h!ng n hiu
sut phn ng.
Nhit l mt trong nhng yu t quan
trng i vi phn ng ankyl ha. S thay i
nhit s lm thay i s l!ng ca cc tm
axit Bronstet [2] v thay i kh nng ehirat
ha ca tc nhn etanol. S thay i nh
h!ng n chuyn ha v chn lc sn
phm ca phn ng; ng thi qu trnh lm
thay i kh nng to cc trn xc tc lm thay
i hot tnh xc tc [3]. Nhit thch hp cho
qu trnh chuyn ha ny l 300 450
o
C.
Tc dng cng nh h!ng rt ln n
chuyn ha benzen v chn lc sn phm
etylbenzen. Khi tc dng nh, thi gian tip
xc ca cht phn ng vi xc tc ln, hi cht
i su vo cc l xp ca xc tc lm tng kh
nng tip xc vi cc trung tm hot ng do
lm tng chuyn ha benzen v lm gim
chn lc sn phm etylbenzen v sn phm ny
d dng i vo phn ng hn so vi benzen. Khi
tc dng ln hn, hi cht i qua vng xc
tc nhanh hn lm gim thi gian tip xc ca
cht vi cc tm hot ng do lm gim
chuyn ha benzen nh!ng s lm tng chn
lc sn phm etylbenzen. Nh! vy, hiu sut
to thnh sn phm etylbenzen cao th tc
dng phi c cc gi tr thch hp.
T l mol gia etanol v benzen cng l mt
trong nhng yu t quyt nh cho hiu sut sn
phm etylbenzen. Nu t l mol ln tc l l!ng
tc nhn ln, do chuyn ha benzen cao
nh!ng chn lc etylbenzen gim v ng!c
li. Kt qu cho thy chuyn ha benzen tng
khi t l mol etanol/benzen tng. Nh! vy, phn
ng khng tun theo c ch Langmuir-
Hinshelwood cn c ch Rideal-Eley li gii
thch kh tt trong tr!ng hp ny [2, 3]. T l
mol etanol/benzen tng nn l!ng etilen v
cacbocation to thnh tng do chuyn ha
benzen tng; ng thi qu trnh thun li cho
vic xy ra cc phn ng th cp to
poliankylbenzen nn chn lc sn phm
etylbenzen gim. Mt im ph hp na trong
tr!ng hp ny l c ch Rideal-Eley ch xy ra
i vi cc zeolit c kch th!c l ln cc
phn t hirocacbon thm d dng khuch tn
v phn ng pha kh vi tc nhn phn ng
trong cc l ca zeolit. Nh! vy, c th ngh
161
rng phn ng ankyl ha benzen bng etanol
trn xc tc 30%H-ZSM-5/HY chy theo c ch
Rideal-Eley.
Hm l!ng xc tc H-ZSM-5 mang ln
zeolit HY cng nh h!ng n qu trnh phn
ng. Qua kt qu thc nghim thu !c nh! trn
thy rng mu xc tc 30%H-ZSM-5/HY l tt
nht cho qu trnh to thnh etylbenzen. iu
ny !c gii thch l do tnh axit ca mu xc
tc ny thch ng cho phn ng ankyl ha. Cn
cc zeolit ban u c tnh axit yu (HY) hoc c
tnh axit qu mnh (H-ZSM-5) nh! nu
phn trn l khng thun li cho phn ng ankyl
ha v nht l cho qu trnh to sn phm
etylbenzen. Do c kch th!c l ln nn xc tc
30%H-ZSM-5/HY to ra nhiu sn phm ph
poliankylbenzen hn so vi ZSM-5. Tuy nhin,
mt iu c bit l th l trong sn phm ph
hm l!ng cc sn phm ietylbenzen,
trietylbenzen kh cao; cc cht ny u l sn
phm c gi tr, d dng chuyn ha thnh
etylbenzen bng phn ng phn b li vi
benzen.
IV - Kt lun
1. kho st nh h!ng ca hm l!ng H-
ZSM-5 mang ln zeolit HY cho phn ng ankyl
ha benzen bng etanol. Kt qu cho thy
30%H-ZSM-5/HY l xc tc c tnh !u vit
nht cho qu trnh iu ch etylbenzen. ng
thi xc nh !c v lc axit ca mu xc
tc 30%H-ZSM-5/HY bng ph!ng php gii
hp NH
3
-TPD. Kt qu cho thy rng xc tc
30%H-ZSM-5/HY ch cha cc tm axit trung
bnh v yu; axit ca cc xc tc theo th t
HY < 30%H-ZSM-5/HY < H-ZSM-5.
2. dng ph!ng php k hoch ha thc
nghim tm iu kin ti !u cho phn ng ankyl
ha benzen bng etanol to thnh etylbenzen
trn cc mu xc tc iu ch !c. Kt qu
tm !c ph!ng trnh hi qui cho hm mc
tiu; iu kin ti !u cho qu trnh l nhit
428
o
C, tc dng 2,66 h
-1
, t l mol
etanol/benzen 0,967. kim tra li phn ng
iu kin ti !u va tm !c v xc nhn rng
ph!ng trnh hi qui thu !c m t ng th
nghim cho. Mt khc, ngh c ch phn
ng ankyl ha benzen bng etanol trn xc tc
30%H-ZSM-5/HY theo c ch Rideal-Eley.
T)i liu tham kho
1. L c Ngc. X l s liu v k hoch
ha thc nghim, i hc Khoa hc T
nhin-i hc Quc gia H Ni (2000).
2. K. A. Becker, H. G. Karge, W. D. Streubel.
J. Catal. Vol. 28, P. 403 - 413 (1973).
3. Pierre Leveque, Le H. Dao. Appl. Catal. A,
Vol. 53, P. 47 - 59 (1996).
4. G. Panagiotis, Smirniotis, Eli Ruskenstein.
Ind. Eng. Chem., Vol. 34(

5), P. 1517 - 1528
(1995).