KHOA HO HC

KHA LUN TT NGHIP

Bc u kho st s hp ph tylen, propen,
iso-butylen trn zeolit chabazite bng phng
php phim hm mt .

(PSeudopotential Plane-Wave Density Functional Theory: PSPW DFT)



Gio vin hng dn : TS L Minh Cm
Sinh vin : Lng Thin Ti K53C


Phn I. t vn
I/L do chn ti
Trong na cui th k XX, lnh vc nghin cu v
ng dng ca zeolit ra i v c nhng bc pht
trin mnh m. Nh c cu trc mao qun ng u,
din tch b mt ln, zeolit c nhiu ng dng, c bit
l trong lnh vc xc tc ho du. zeolit c s dng
lm xc tc c hot tnh v chn lc cao, d tch ra
khi sn phm v khng gy nhim mi trng
Trong zeolit, cc tm axit Bronsted l cc tm c
hot tnh xc tc, tuy nhin nhng hiu bit chi tit v
c ch ca nhng phn ng (cracking,izome ha, ankyl
ha,) xy ra trn cc tm ny cn rt hn ch.
Chnh v vy vic nghin cu s hp ph v chuyn
ha ca cc hirocacbon trong cc mao qun ca cc
axit zeolit aluminosilicat c bit c cc nh khoa hc
thc nghim cng nh l thuyt quan tm.


I/L do chn ti
- Ngy nay vi s pht trin ca my tnh in t, ha hc l
thuyt c coi nh mt cng c rt hu hiu cho vic nghin
cu xc tc. Trong khi , vic xy dng 1 h thng thc
nghim c th xc nh c s phn b sn phm trong
tng bc phn ng thc s l mt thch thc i vi cc nh
khoa hc thc nghim.

- Mc d nhng khi nim c bn v proton ha anken trn zeolit
c nghin cu nh tnh ton ha hc lng t nhng
mc l thuyt khc nhau

, song vn cn nhng cu hi lin
quan n c ch hnh thnh, bn, nng lng hot ha,

- Bc u kho st qu trnh hp ph ca etylen, propen, iso-
butylen trn zeolit Chabazite bng phng php phim hm mt
.
II. i tng nghin cu
Zeolit l cc aluminosilicat tinh th M
2/n
.Al
2
O
3
.xSiO
2
.yH
2
O
M l cation c ha tr n (hay cation b tr in tch khung)
x l t s mol SiO
2
/Al
2
O
3

y l s phn t H
2
O

kt tinh trong zeolit.\

n v cu trc ca zeolit l cc t din TO
4
(T= Al,Si)



















2-
O Si
4+
O
2-
O
2-
O
2-
2-
O Al
3+
O
2-
O
2-
O
2-
Thay Si = Al
III.Nhng gii php khoa hc c gii quyt

a, Thut ton: M phng h bng ct cluster, phng
php hay s dng l HF, DFT vi cc b hm khc
nhau








Hnh 2: M phng qu trnh ct cluster t zeolit

Si
O
Si
O
Al
O
Si
O Si
O
Si
O
Si
O
Si
O
-
O
-
O
-
O
-
O
-
O
-
O
-
O
O
-
O
-
O
-
O
O
-
O O
-
-
O
O
-
H
Si
Si
O
-
O
-
O
-
O
-
O
-
O
- Al
O
O
O
Si
H H
H
O
Si
H
H
H
H
H
III.Nhng gii php khoa hc c gii quyt
b, Ni dung khoa hc: Cc kt qu nghin cu thc
nghim v l thuyt ch ra rng: s proton ha anken
qua 2 giai on, v cui cng to thnh ankoxi b
mt, trong cacbocation ch tn ti nh l mt trng
thi chuyn tip

-Bc 1: to phc gia proton v anken.
-Bc 2:hnh thnh lin kt C-O (nguyn t O
bn cnh nhm OH trong mng zeolit) to
phc
H
2
C
1
=C
2
R
1
R
2
+
O
Ha
Al
O
H
2
C
1
= C
2
R
1
R
2
O
Ha
Al
O
O
Al
O
C
2
C
1
R
1
R
2
O
Al
O
C
2
C
1
H
2
Ha
R
1
R
2
(II)
(III)
(IV)
(I)
O
Al
O
CH
2
C
Ha
(III')
R
2
R
1
O
Al
O
CH
2
C
(IV')
R
1
R
2
Ha
H
H
Ha
Hnh 3: S
m phng cc
giai on trong
qu trnh hp
ph.
(I) l trng thi
ban u ca h
(II) l phc pi,
(III) l trng thi
chuyn tip,
(IV) l phc

III.Nhng gii php khoa hc c gii quyt
Hn na kt qu tnh l thuyt cn cho bit:
Kh nng hp ph ca cc anken:
etylen > propen > iso-butylen.
Xc nh c cc cu trc hnh hc trong qu
trnh v tnh c nng lng km theo.
IV.Nhng vn tn ti cn nghin cu
H cht nghin cu c s lng nguyn t rt ln, i km
vi n l mt lng php tnh khng l, nn phi p
dng mt lot cc php n gin ha, v vy dn n

- H m phng cha st vi h thc v h m phng
cha l h v hn tun hon, v h m phng cluster c
xy dng t mt phn h thc do khng th hin c
tt c cc nh hng ca zeolit n h cht nghin cu.
- Cc phng php tnh c chnh xc mc tng
i
- i vi trng hp isobutylen vn cn nhiu vn
cn tranh lun. C tc gi ch ra rng khi iso-butylen hp
ph trn zeolite th dng tn ti ch yu li l cation tert -
butyl
Phn II. Gii quyt vn .
Mc tiu cng trnh: kho st c ch proton
ha anken
Nhim v c th:
Xy dng m hnh h (v hn tun hon)
Ti u ho hnh hc cc h nghin cu.
Tnh nng lng cc qu trnh lin quan bao
gm:
+ Nng lng hnh thnh phc
+ Nng lng hnh thnh phc
So snh kh nng hp ph ca anken v s
nh hng hp ph.









Xy dng m hnh h
Ti u ha cu trc
Cu trc hnh hc Nng lng
Nhn xt v kt lun
Phng php nghin cu

Xy dng h cht nghin cu v hn tun hon
ng vi cu trc ca h thc
p dng phng php phim hm mt , s
dng gi th v b hm sng phng (phng
php PSeudopotential Plane-Wave DFT)
trn phn mm Nwchem nghin cu h cht

Phng php phim hm mt l mt phng php tnh t u
(ab-initio) hin i, cng vi s dng b hm sng phng l b hm
p dng rt tt cho h tun hon. Trong khi , vic p dng gi
th cho php gim khi lng tnh ca h




* Ti u ho cc anken etylen ,propen v iso-butylen.

Bng 1: Cc thng s ca etylen tnh c t l
thuyt v thc nghim


d
C=C
d
C-H
Gc HCC Gc HCH
Tnh c t l
thuyt
1.32 A
0
1.08A
0
121.7
0
116.7
0

Thc nghim
[*]
1.33 A
0
1.08 A
0
121.7
0
116.6
0

(*) c tra t cc gio
trnh hu c

Phn II:Ni dung nghin cu v kt qu

Xt ring cc anken

d
C1=C2
d
C1-H
d
C2-H
d
C2-C3

Tnh c
t l thuyt
1.32 1.082 v
1.087
1.09 1.48
Thc
nghim [*]
1.34 1.081 v
1.091
1.09 1.50
Bng 2: Cc thng s ca propen tnh c
t l thuyt v thc nghim
d
C1=C2
d
C1-H
d
C2-CH3

Gc HC1C2
PSPW
DFT/Nwchem
1.32 1.08 1.48 120.87; 121.21
B3LYP 6-31G(d)/
Gaussian 98
1.34 1.09 1.51 121.76
Bng 3: Cc thng s ca iso-butylen tnh c t l thuyt: phng
php nghin cu PSPW DFT phn mm Nwchem, v phng php
B3LYP/6-31G(d) phn mm Gaussian 98
phng php PSPW DFT/Nwchem cho kt qu rt
gn vi thc nghim v vi kt qa tnh l thuyt ng tin cy
khc
tin cy ca phng php nghin cu
Chabazite
c ti u ha

Xt h Chabazite ring l
Ti u ha Chabazite: d(O-H
a
) = 0.992 A
0

nng lng -428.3239 hartree
Xt cc h anken - Chabazite
Xy dng m hnh h nghin cu (t cc anken li gn tm
axit Bronsted: H
a
)
Hnh 2: Input h
tylen - Chabazite

* Ti u ho h anken chabazite
Cu trc v nng lng
phc , phc

Nhn xt v kt lun























Hnh 3: output phc
ca propen chabazite



Hnh 3: output phc ca
propen chabazite



Etylen Chabazite Phc Phc
d
O-Ha
(A
0
) 0.992 0.984 1,10 1.02
d
Ha-C2
(A
0
) 1.98
d
Ha-C1
(A
0
) 1.91
d
C1-C2
(A
0
) 1.316 1.34 1.323 1.34 1.47 1.50
d
O2-C2
(A
0
) 2.85 1.60 1.46
Gc AlOH 103.95
0
94.53
0

Nng lng h
(hartree)
-13.6816 -428.3239 -442.0238 -442.0515
Bng 4: Kt qu tnh cho qu trnh hp ph ca etylen
Ch s in m, bn phi l kt qu tnh theo phng php DFT:LDA/DND
(constrained cluster)

Bng 5: Kt qu tnh cho qu trnh hp ph ca propen

Ch s in m bn phi l kt qu tnh theo phng php HF/6-31G
*

(Constrained cluster) [3]

Propen Chabazite
Phc
Phc
(spc)
Phc (spp)
d
O-Ha
0.992 0.954 1.15 0.96
d
Ha-C2
1.99
d
Ha-C1
1.78
d
C1-C2
1.32 1.32 1.34 1.32 1.48 1.52 1.49
d
O2-C2
3.12 1.69 1.49 1.58
Gc AlOH 103.95
0
93.65
0

Nng lng h
(hartree)
-20.5565 -428.3239 -448.9025 -448.9197 -448.9169
Bng6: Kt qu tnh cho qu trnh hp ph ca iso-butylen
Ch s in m bn phi l kt qu tnh theo phng php HF/6-31G
*

(Constrained cluster) [3]

Isobutylen Chabazite
Phc
Phc
(spc)
Phc
(spp)
d
O-Ha
0.992 0.954 1.74 0.96
d
Ha-C2
1.92
d
Ha-C1
1.19
d
C1-C2
1.32 1.32 1.39 1.33 1.44 1.52 1.48
d
O2-C2
3.53 2.66 1.52 1.62
Gc AlOH 103.95
0
92.66
0

Nng lng h
(hartree)
-27.4311 -428.3239 -455.7901 -455.8004 -455.7887
E to phc
(kJ/mol)
(Nng lng
hp ph )
E to phc (kJ/mol)
(Nhit hp ph)
E( - ) (kJ/mol)
spc spp (nu c) Spc spp (nu c)
H etylen -CHA -48.02 -120.71 -72.69
H propen-CHA -57.99 -103.13 - 95.78 -45.14 -37.79
H Isobutylen -CHA -92.10 -119.13 -88.43 -27.03 3.67
Bng 7: Nng lng km theo cc qu trnh
Nhn xt:
S hnh thnh phc v nng lng hp ph
Cc tham s ti u ha ca anken hp ph v lin kt OH
a
trong
phc l gn tng t (hoc thay i khng nhiu) so vi gi tr
tnh ton ca tng h ring bit (anken v OH
a
trong Chabazite).
di lin kt C=C v O-H
a
trong phc di hn so vi d(C=C)
trong anken ring l, v d(O-H
a
) trong Chabazite ring l l
khong 0.003 A
0
v 0.11 A
0
(i vi h etylen Chabazite) v
0.02A
0
v 0.16A
0
(i vi h propen Chabazite) .
iu ny chng t rng cc di ca c 2 lin kt u yu i
(nhng khng mnh) v gi tr gc lin kt AlOH
a
b thay i do
proton ca cc tm hot ng nh hng v pha lin kt i ca
anken (t 103.95
0
xung cn 94.53
0
i vi phc ca h etylen-
Chabazite v 93.65
0
i vi phc ca h propen Chabazite).


Ring i vi trng hp ca isobutylen, trong phc ta thy
rng di lin kt C=C tuy khng tng ng k (tng t
1.32A
0
trong iso-butylen ln 1.39A
0
trong phc ), nhng
khong cch O-H
a
li tng mnh (t 0.992A
0
ln 1.74A
0
) iu
ny c gii thch l do proton H
a
rt d to vi iso-butylen
thnh cacbocation tert-butyl bn, nn s tc ng ca iso-
butylen ln tm Bronsted H
a
l rt ln, lm ko di lin kt O-
H
a
v lm ngn lin kt H
a
-C
1
(1.19A
o
) so vi cc trng hp
elylen v propylen

Thng thng, proton ca nhm OH
a
l gn vi nguyn t C1
(cacbon u mch) hn l vi nguyn t C2 (cacbon s tng tc
vi tm axit). Thc t tnh ton cng ch ra iu :
Vi phc ca h etylen CHA : d(H
a
-C1)=1.91 A
0
d(H
a
-C2)
=1.98A
0
v vai tr ca 2 nguyn t C1 v C2 l tng ng.
Vi phc ca h propen CHA : d(H
a
-C1)= 1.32 v d(H
a
-C2)
=1.78 A
0

Vi phc ca h iso-butylenCHA: d(H
a
-C1)= 1.19 v d(H
a
-C2)
=1.39 A
0

Khi i t etylen propen iso-butylen ta thy rng khong
cch d(H
a
-C1) gim dn (t 1.91 1.32 1.19A
0
) iu ny chng t
lin kt gia cc anken v H
a
trong phc ngy cng bn, iu ny
cng c chng t qua kt qu nng lng hnh thnh phc
(nng lng hp ph) m dn khi i t etylen propen isobutylen.
Nng lng hp ph ca etylen l -48.02 (kJ/mol) ca propen l
-57.99 (kJ/mol) v ca iso-butylen l -92.10 (kJ/mol).

Nhn xt
*S hnh thnh phc (ankoxi) v nhit hp ph.
Khi nghin cu nh hng ca di mch C n qu trnh hp
ph ca hirocacbon, yu t quan trng nht khng phi l kch
thc h m l bn cht ca C trong lin kt cng ha tr C-O.
Khi i t phc n phc , di d(C2-O2) gim dn n
di ca mt lin kt n (t 2.85 n 1.60 A
0
i vi h etylen
Chabazite, t 3.12 n 1.69 A
0
i vi h propen Chabazite).
Nh vy trong cc phc c s hnh thnh ankoxi b mt.
Ring trong trng hp phc ca h isobutylen Chabazite,
d(C2-O2) sn phm chnh l tng i ln (2.63A
0
), iu ny c
th a ra nhn xt rng trong qu trnh hp ph ca iso-butylen
trn chabazite, dng tn ti ch yu s l cc cabocation tert-butyl
tng ng m khng phi l ankoxi bc ba (iso-butoxi).









Khi i t etylen propen, di lin kt d(C2-O2) trong phc
tng t 1.60A
0
n 1.69A
0
iu ny chng t ankoxi bc mt
trong phc ca h etylen Chabazite l bn hn ankoxi bc
hai trong phc h propen Chabazite.
Nhit hp ph ca cc anken trn Chabazite l tng i
ln, v vy Chabazite c kh nng hp ph mnh cc anken.
Tuy nhin khi i t etylen propen , nhit hp ph ln dn, t -
120.71 (etylen) n -103.13 (propen) , khuynh hng ny lin
quan trc tip n bn ca lin kt cng ha tr C-O, phn
nh qua gi tr d(C2-O2). C th rt ra kt lun v bn ca
cc ankoxi gim theo chiu tng mch carbon: etoxi > propoxi.
Ring trng hp iso-butylen c ch hp ph khng nh 2
trng hp trn v khng to ra ankoxi nn ta khng th so
snh.
Nhn xt
*S nh hng hp ph
- Vi nhit hp ph propen v nhit hp ph isobutylen: nng
lng ca s to thnh ankoxi bc cao m hn s to thnh ankoxi
bc thp, chng t s hp ph d to ankoxi bc cao. Hn na trong
phc ca h propen chabazite v h isobutylen chabazite th d
Ha-
C2
< d
Ha-C1
, iu ny chng t H
a
s tn cng chnh vo cacbon bc
thp v to thnh ankoxi bc cao hn.
Tuy nng lng hp ph to thnh ankoxi bc cao khng m
hn nhiu ankoxi bc thp, nhng thc t th sn phm chnh ca qu
trnh hp ph l ankoxi bc cao, v s hp ph trong zeolit cn ph
thuc vo nhiu yu t, m hiu ng khng gian l mt yu t rt
quan trng. H
a
s d tn cng vo nguyn t C t b n ng hn, tc l
C1, to thnh ankoxi bc cao.

Nhn xt
*nh hng ca di mch C ln qu trnh hp
ph.
Khi di mch C ln dn t C
2
(etylen) C
3

(propen) C
4
(isobutylen):
bn ca phc tng dn, do di d(H
a
C1) gim
dn (1.91 1.32 1.19A
0
) v nng lng hp ph nh dn
, -48.02 (tylen) , -57.99 (propen) v -92.10 (iso-butylen)
bn phc gim dn t etoxi n propoxi,do di
d(C2-O2) tng dn, nhit hp ph tng dn:t -120.71
(etylen) n -103.13 (propen)

* D on ng phn ng:

Kho st ph mt trng thi DOS
Mt s pic trong ph DOS ca propen b bin mt hoc l b dch
chuyn,chng t trong trng thi (II) propen khng cn trng thi t
do m i vo trng thi lin kt (phc )

Kt lun
Tnh c cc cu trc ca cc anken: etylen v propen,
cho kt qu rt gn vi thc nghim.
Kho st kh nng hp ph ca tylen, propen v iso-
butylen trn Chabazite. Xc nh c s tn ti ca cc
cu trc phc v phc trong qu trnh hp ph. So
snh bn ca cc phc ny theo chiu di mch cacbon
ng thi tnh c gi tr nng lng ca cc qu trnh
km theo.
Ch ra kh nng hp ph ca etylen l cao hn ca propen,
ca propen.Trong trng hp anken bt i xng, sn
phm chnh l ankoxi (hay cacbocation) bc cao hn.
Qua cc d kin v nng lng ca qu trnh hp ph, ta
c th d on ng phn ng

Chng minh c s to thnh phc v phc qua ph DOS
v qua phn tch cc gi tr v di lin kt.
T cc kt qu thu c, ta thy kh nng p dng tt ca
phng php PSeudopotential Plane Wave DFT (PSPW DFT)
khi nghin cu cc h v hn tun hon, t chng ti xut
tip tc dng phng php ny nghin cu y v su sc
hn na s hp ph v chuyn ha cc anken trn zeolit
Chabazite. V d nh trong lun vn cn cha cp n nhng
nh hng t cu trc zeolit, nh t l Si/Al, dn n s lng
tm axit Bronsted, vic c mt ca cc nguyn t khc trong
zeolit (v d nh thay th Si bng B, Ga thay v l Al), nh
hng t bn cht zeolit (nghin cu s hp ph trn cc zeolit
khc) , vi hi vng tm hiu c ch ca qu trnh, d on
c cc ng phn ng chnh, gip cc nh thc nghim nh
hng c tin trnh phn ng.