M U

Trong na cui th k XX ngi ta chng kin s ra i v pht trin mnh m ca mt

ngnh cng ngh mi. l lnh vc nghin cu v ng dng cc Zeolt, c bit l trong cng
ngh Lc-Ho Du. Zeolt c s dng lm cht xc tc c hot tnh v chn lc cao, d tch
khi sn phm v khng gy nhim mi trng. Vi nhng u im nh vy n thc y nhiu
nh khoa hc i su vo bin tnh v tm kim nhng Zeolt mi nhm mc ch a vo ng dng
xc tc trong cng nghip [8].
Xc tc Cracking hin ang i u vi hai thch thc ln:
1. Yu cu nghim ngt v mi trng i hi xng Cracking vn m bo ch s octan cao
nhng khng cha hp cht ca ch v gim ti thiu hm lng hydrocacbon thm.
2. Cng nghip ho du pht trin mnh i hi mt ngun nguyn liu di do m quan trng
l cc olefin.
Ngy nay, hu ht cc cht xc tc Cracking du m u cha hai hp phn chnh l Zeolt v
cht nn (matrix). S ni tri ca Zeolt vi vai tr l mt cht thm nh hng cho vic tng ch
s octan v tng hiu sut to olefin. c tnh ca Zeolt l din tch b mt ring kh ln, h thng
mao qun ng u, axit v ng u cao, kh nng chn lc hnh dng rt tt [2]. y l mt
trong nhng vt liu v c mao qun l tng trong tng lai.
Vit Nam, ngnh cng nghip lc ho du ang bt u xy dng. Cc quy nh v s
dng xng khng pha ch trong ton quc cng ang c thc thi. Tnh hnh ny i hi mt nhu
cu rt cao c v s lng v cht lng ca xc tc Cracking. Vit Nam l nc c tim nng ln
v nguyn liu ch to xc tc Cracking (cc m khong st, t himvi tr lng di do).
Trong khi s lng nghin cu v xc tc Zeolt cng nh hot tnh ca Zeolt cn hn ch. Do
vy, iu ch v nghin cu xc tc cho phn ng l mt trong nhng vn quan trng v c
ngha rt ln v mt khoa hc, thc tin v mang tnh thi s.
Do , trong khun kh bn n ny em iu ch v nghin cu hot tnh ca cc xc tc
ZeoltX, ZeoltY, ZeoltP trn phn ng Cracking hydrocacbon (n-Hecxan).
Hy vng rng, vi s pht trin ca khoa hc k thut cng vi vic cng nghip ho, hin i
ho t nc, vic ng dng xc tc Zeolt s lm gp phn ng k trong cng cuc xy dng t
nc.

30

PHN I:
TNG QUAN TI LIU
I. Tng quan v Zeolt
I.1. S lc lch s v s pht trin ca Zeolt .
Zeolt bt u c pht hin vo nm 1756 n nay hn 3 th k. Nm 1756, Le Bron
Bronstedt [13] l mt nh khong hc ngi Thy in pht hin ra mt loi khong mi vi tn
gi l Zeolt, theo ting Hy Lp Zeo: si, Lithot: , v vy Zeolt cn c ngha l si.
ng pht hin c Zeolt nh hi nc thot ra khi nung khong ny. Tuy nhin mi n th
k sau Zeolt mi bt u c nghin cu k phng th nghim.
Vo nm 1932, Mac Bai [14] lm r hiu ng Ry phn t, sau vo nm 1944, Barrer
v Ibbitson ch ra rng hiu ng ny cho php tch cc n v iso parafin.
Bt u t thi im cc loi Zeolt c phc v cho cng nghip. n nm 1956 ngi ta
mi tng hp c cc loi Zeolit u tin.
Vo nhng nm cui th k XX ny s hiu r v Zeolt tng i su rng. n nay c hn
35 loi Zeolt t nhin c tm thy v rt nhiu Zeolt tng hp c ra i [5].
Vic nghin cu cc mt Zeolt ngy cng tng. Hin nay c khong hn 15.000 cng trnh
cng b v hn 10.000 pht minh sng kin v tng hp Zeolt c v cu trc v ng dng n.
c bit ring trong nm 2000 n nay c hn 1060 loi Zeolt tng hp mi ra i.
Nh vy, Zeolt c tm quan trng ln lao trong khoa hc v k thut. Trong tt c cc loi
Zeolt hin c, ngi ta bit r thnh phn, tnh cht ng dng, cu trc mng tinh th ca nhiu
loi Zeolt t nhin v Zeolt tng hp nh: Zeolt A, Zeolt Y, Zeolt X, Zeolt ZSM-5, Zeolt ZSM11,
I.2. Gii thiu v Zeolt
I.2.1. Khi nim v phn loi.
I.2.1.1. Khi nim.
Zeolt l hp cht v c dng aluminosilicat tinh th c cu trc khng gian ba chiu, l xp
c bit v trt t cho php chng phn chia (Ry) phn t theo hnh dng v kch thc. V vy,
Zeolt cn c gi l hp cht ry phn t.
Thnh phn ch yu ca Zeolt l Si, Al, Oxi v mt s kim loi kim, kim th khc.
Cng thc chung ca Zeolt l:
M2/nO . Al2O3 . x SiO2 . y H2O
Trong :

M: Cation c kh nng trao i.

n: Ho tr ca cacbon.
x: T s mol SiO2/Al2O3.

30

y: S phn t nc trong n v c s ( khong t 1 12 ).

T s x 2 l s thay i i vi tng loi Zeolt cho php xc nh thnh phn v cu trc ca
tng loi.
V d: Zeolt A c x = 2.
Zeolt X c x = 2,3 3.
Zeolt Y c x = 3,1 6.
Mordenit tng hp c x 10. c bit cc Zeolt h pentasit c x=201000. Ring i vi
Zeolt ZSM-5 c tng hp dng cht cu trc c 7x200.[16]
Gn y ngi ta tng hp c cc loi Zeolt c thnh phn a dng c t l mol
SiO2/Al2O3 cao thm ch c nhng loi cu trc tng t Zeolt m hon ton khng cha cc
nguyn t nhm nh cc silicatic
I.2.1.2. Phn loi Zeolit.
C nhiu cch phn loi Zeolt nhng thng thng ngi ta phn loi theo ngun gc, kch
thc mao qun v theo thnh phn ha hc.
Theo cch ny c 5 nhm:

Zeolt ngho Silic hoc nhm.

Zeolt trung bnh Silic.

Zeolt giu Silic.

Ry phn t Silic.

Zeolt bin tnh.

+ Phn loi theo ngun gc:

C 2 loi: Zeolt t nhin v Zeolt tng hp.
- Zeolt t nhin thng km bn v do thnh phn ho hc bin i ng k nn ch c mt vi
loi Zeolt t nhin c kh nng ng dng thc t nh: Analcime, chabazite, hurdenite,
clinoptilonit... v chng ch ph hp vi nhng ng dng m khng yu cu tinh khit cao. [4]
- Zeolt tng hp nh: ZeoltA, ZeoltX,ZeoltY,ZeoltZSM-5,ZSM-11... Zeolt tng hp c
thnh phn ng nht v tinh khit, a dng v chng loi nn c ng dng rt rng ri trong
cng nghip cng nh trong nghin cu.
+ Phn loi Zeolt theo kch thc mao qun:
Vic phn loi Zeolt theo kch thc mao qun rt thun tin cho vic nghin cu ng dng
Zeolt, theo cch ny ta chia Zeolt ra lm 3 loi:
-

Zeolt c mao qun rng: ng knh mao qun t 7A0 n 8A0.

Zeolt mao qun trung bnh: t 5A0 n 6A0.

Zeolt mao qun hp: di 5A0

30

+ Phn loi Zeolt theo thnh phn ho hc:

Zeolt giu Al: l loi Zeolt c t s SiO2/Al2O3 2.

Theo quy lut Lowenstein xc nh rng: Trong cu trc Zeolt hai nguyn t Al khng th tn
ti ln cn nhau. Ngha l trong cu trc Zeolt khng th tn ti cc lin kt Al-O-Al, m ch tn ti
cc lin kt -Si-O-Si- v -Si-O-Al-. Do vy, t s SiO 2/Al2O3 l gii hn di khng c t s
SiO2/Al2O3 < 2 [4]. Khi t s ny gn 2 th Zeolt c coi l giu nhm.

Zeolt silic trung bnh:

Vi Zeolt loi ny t l SiO 2/Al2O3 = 4 5 v c th ti 10. Zeolt thuc h ny l ZeoltX,

ZeoltY, Sabazit ( 2,15 )...

Zeolt giu silic:

Loi ny tng i bn nhit nn c s dng trong nhiu qu trnh xc tc c iu kin khc

nghit, l cc Zeolt thuc h ZSM, c tm ra bi hng Mobil, t l (SiO 2/Al2O3) = 20 200,
ng knh mao qun t 5,1 A0 n 5,7 A0, cu trc khung ca ZSM thng c khong 10 nguyn
t Al tng ng vi 1000 nguyn t Si trong mng. Ngoi ra c rt nhiu Zeolt tng hp khc c t
s Si/Al cao c tng hp nh s c mt ca cht to cu trc (Template ) h amin bc 4: R4N+.

Ry phn t Silic.

L loi vt liu c cu trc tinh th hoc tng ng nh aluminosilicat tinh th nhng hon ton
khng cha nhm. Vt liu ny k nc v khng cha cc cation b tr in tch (hon ton khng
c tnh cht trao i ion).

Zeolit bin tnh.

L Zeolt sau khi tng hp c ngi ta c th dng cc phng php bin tnh bin i
thnh phn ho hc ca Zeolt. V d nh phng php tch nhm ra khi mng li tinh th v
thay th vo l Silic hoc nguyn t c ho tr 3 hoc ho tr 4 gi l phng php tch nhm.
Theo tc gi [17] s phn loi Zeolt tng hp theo thnh phn ho hc c thng k trong
bng 1.
Vic phn chia Zeolt theo t s SiO2/Al2O3 c coi l mt c trng quan trng nh hng n
cu trc, tnh cht l ho hc ca Zeolt.

Bng 1: s bin i tnh cht ca Zeolit khi t s SiO2/Al2O3 .

t s SiO2/Al2O3
1. Tnh cht bn nhit tng t (7001300)0C

30

2. Cu trc thay i t vng 4,6,8 n vng 5.

3. Tnh cht b mt t a nc n k nc .
4. Lc axt trn tng tm axt tng.
5.Dung lng trao i ion gim.
I.2.2. Cu trc ca Zeolt .
I.2.2.1. c im cu trc ca Zeolt .
Zeolt c cu trc tinh th, cc Zeolt t nhin cng nh Zeolt tng hp c b khung c to
thnh bi mng li khng gian 3 chiu ca cc t din TO4 ( T l Si hoc Al ).
Mi t din TO4 c 4 ion O2- bao quanh mt cation T(Si, Al). Mi t din lin kt vi 4 t din
bn cnh bng cch gp chung cc nguyn t oxy nh [18]. Trong t din AlO 4 c ho tr 3
nhng s phi tr l 4 nn t din AlO4 mang mt in tch m.
in tch m ny c b tr bng cation kim loi, cn gi l cation b tr in tch khung v
thng l cation kim loi kim. V vy, s cation kim loi ho tr 1 trong thnh phn ho hc ca
Zeolit chnh bng s nguyn t nhm (Al).
n v cu trc c bn ca Zeolit l cc t din TO4 chng c biu din hnh 1:

n v

cu

Cc
Unit) v cc khi a

T din AlO4
Hnh

O-2

-1

SiO4

T din

1:

trc

c bn ca Zeolt.

SBU

(Secondary Building

din trong Zeolt c trnh

by cc hnh 2 v 3.

Cc n v cu trc th cp SBU, c to ra do s lin kt cc t din TO 4 theo mt trt t xc

nh v tun theo quy tc thc nghim-Lowenstein.

S4R

S6 R

D4R

D6R

30

(4-1)

(5-1)

(4-1-1)

Hnh 2: Cc n v cu trc c th cp (SBU) trong cu trc Zeolit

Hnh 3:Mt s a din c trong zeolt

Cc n v cu trc th cp SBU c th l cc vng oxy gm cc vng 4, 6, 8, 10, 12cnh
hoc cc vng kp 4x2, 6x2, 8x2, vvTu theo cch ghp ni cc SBU theo kiu ny hay kiu kia
m s to ra cc loi Zeolt khc nhau [32]. Hnh 4 ch ra cch ghp ni cc n v cu trc to ra
Zeolt.

Hnh 4: cc n v cu trc v cch ghp ni to ra Zeolit.

I.2.2.2. Phn loi cu trc Zeolit [12]
Da trn c s hnh hc ca khung cu trc Zeolt, Smith, Fisher v Meier, Breck phn loi
Zeolt thnh 7 nhm n v SBU. Mi SBU c trng cho mt cch sp xp ca t din TO4. 7
nhm phn loi l:

30

Bng 2: Nhm n v cu trc s cp.

Nhm
1
2
3
4
5
6
7

n v cu trc s cp (SBU)
Vng 4 cnh n, S4R
Vng 6 cnh n, S6R
Vng 4 cnh kp, D4R
Vng 6 cnh kp, D6R
T hp 4-1, n v T5O10
T hp 5-1, n v T8O16
T hp 4-4-1, n v T10O20

Phng php phn loi ny cho php d dng m t cu trc Zeolt bng cc n v cu trc a
din.
I.3.3. Cu trc knh trong Zeolt .
Cc sodalit ghp ni vi nhau to thnh mt khoang rng cc ca s to, nh khc nhau, nh
m Zeolt c cu trc xp. Tp hp khng gian rng tun theo mt quy lut nht nh s cu to
cu trc knh ca Zeolt. Bn cht ca h mao qun trong Zeolt dehydrat ho l rt quan trng, n
xc nh tnh cht vt l v ho hc ca Zeolt Trong cc Zeolt c 3 loi h thng mao qun nh
sau:
* H thng mao qun mt chiu: Cc mao qun khng giao nhau thuc loi ny c h Analeim
(hnh 5).

Hnh 5: H thng mao qun 1 chiu khng giao nhau trong Zeolit.

o
o
o

Hnh 6: H thng mao qun 2 chiu trong khung Zeolt.

30

* H thng mao qun 3 chiu, c cc mao qun cng chiu, ng knh ca cc mao qun bng
nhau v khng ph thuc vo hngV d faujasit (X,Y,A) (hnh 7,8).

Hnh 7 :H thng mao qun 3 chiu trong khung zeolt X(a) v Y(b)..

Hnh 8: H thng mao qun 3 chiu trong zeolt.

I .3 Cu trc mt s zeolit cn nghin cu.
I.3.1 Cu trc Zeolt X v Zeolt Y.
Zeolt Y c Breck ( hng carbide) pht minh vo nm 1964 [20].

30

Trong cu trc zeolt X, zeolt Y,cc lng sodalit c dng bc din ct c sp xp theo kiu
kim cng Hnh 8 .Mi nt mng ca zeolt X, zeolt Y u l cc bt din ct v mi bt din ct
lin kit mt bc din ct khc 6 cnh thng qua lin kt cu oxy s mt 6 cnh ca bc din
ct l 10 .Do vy, tn ti 4 mt 6 cnh cn trng ca mi bt din ct trong zeolit X, Zeolt Y.

Hnh 9: cu trc tinh th ca Zeolt X v Zeolt Y

S t din Si04 v Al04- trong mt mng c s ca zeoltX, ZeoltY l 192,s nguyn t oxy l
384.S phn bit gi zeolitX v zeoltY da vo t
s Si02/Al203 . Nu t s ny bng 2 3 th ta c zeolt X , cao hn ta s c zeolt Y.
Cng thc ho hc ca mt s mng c s ca zeolt X v zeolit Y nh sau.
Zeolit X

Na86 [(Al02)86.(Si02)106].260 H20 .

Zeolit Y :

Na86 [(Al02)56.(Si02)136].260 H20 .

Nh vy, zeolt X giu nhm hn zeoltY mt d tng cc cation Si 4+ v Al3+ u bng 192 v
bng s nh ca mt mng c s ( mi nh ca mt bt dn ct l Si hoc Al ).
V t s SiO2/Al2O3 zeolt Y ln hn zeolt X nn d bn c nhit ca zeolt Y cao hn zeolt
X ,do s to thnh lin kt gia cc mt zeolt X v zeolt Y khc vi zeolt A nn cu trc cng
khc .ng knh ca zeolt X v zeolt Y khong 12,7 A0 .
Do lin kt cc mt 6 cnh nn tng ti ba dng ca s tng ng vi cc mt thng nhau vi
cc hc . Khi hai hc thng nhau ca s trong trng hp ny l ln nht vi vng 12 oxy kch
thc 7,8 A0. Khi cc hc thng vi nhau qua ca s , trong trng hp ny c vng 6 oxy v kch
thc 2,2A0 [1]
I.3.2 cu trc zeolt P .
Zeolt P l loi zeolt c kch thc mao qun b c kh nng hp ph kh . Xc tc zeolt P c
cng thc ho hc l .
Na20.Al203.2,5.Si02.5H20 .

30

Bng 3 : Mt s thng s c bn ca zeolt

Stt
1
2

Thng s
T l = Si02 / Al203
n v

Kch thc mao qun

hp ph phn t c kch thc max

[9].

Gi tr
1,1 2,5
S4R (Vng 4 cnh song song)
Theo hai hng a v b l :
(3,4 4,4)A0 v (2,8 4,9)A0
H20

Hnh 10 : cc cu trc ca zeolt P.

I.4. Gii thiu cc phng tng hp zeolt .
c rt nhiu cng trnh nghin cu cng b v cc phng php tng hp zeolt .Vic tng
hp zeolt i t ngun nguyn liu ban u gm hai ngun Si v Al ring l,hoc c th i t
khong st t nhin . Zeolt c hnh thnh trong qu trnh thu nhit nhit t (50 300) 0C
[4].
Di y s gii thiu v qu trnh tng hp zeolt t hai hng k trn
I.4.1 Tng hp zeolt i t ngun Si v Al ring l .
T ngun Si v Al ban u trong hai dung dch ring l, sau khi trn ln chng vi nhau trong
mi trng c nhit v PH nht nh , gen aluminosilicat s c hnh thnh . S hnh thnh gen
l do qu trnh ngng t cc lin kt Si -0H v Al - 0H to ra cc lin kt mi Si - 0Si,Si
0 Al di dng v nh hnh. Sau gen c ho tan nh cc tc nhn khong ho (0H - ,F- ) to
nn c n v cu trc th cp (SPU).Trong cc Iu kin thch hp (nh cht to cu tr , nhit

30

, p xut ) . Cc SPU s lin kt vi nhau to nn cc mm tinh th ri cc mm ny ln dn ln

thnh cc tinh th hon chnh ca zeolt Hnh 11.
Ngun Si, Al (P, Ga, Fe, Ge,B...)
Cc ion khc

Nguyn liu
Qu
trnh
gel
ha

H2O

Tinh thZeolit

T,C
50 - 300
Gel v nh
hnh
Ha
tan gel

Cht khong ho

Qu trnh
Tc nhn to
to mm
cu trc
l n ln
ca tinh
th
Na, K
TMA,TPA
N c

n vcu trc (Si hoc Al)

Hnh 11:S qu trnh tng hp zeolt t hai ngun Si v Al ring l .

Tu thuc vo cc kt ni ca cc SBU chng ta s thu c cc kt ni c cu trc tinh th
khc nhau .Hnh 10 m t cch ghp ni giu cc SBU v qu trnh to mm ln ln ca tinh th .
Nu bc din ct c ni vi nhau qua mt t din ta s c zeolt c cu trc tinh th loi zeolt
A , cn ni qua mt 6 cnh s c loi Zeolt Y [ 7] .
Ngun cha zeolt ban u thng c s dng Na 2Si03 , Si02 gel hoc Si02 sol , (R0)4Si v
ngun Al thng l NaAl02 , Al2 (S04)3 Thnh phn hn hp tng hp thng biu din thng qua
cc t l 0H- / Si02 ; Na+/ Si02 ,R4N+/ Si02 ,,Si04 / Al203 .

30

Bng 4 : Trnh by cc Iu kin tng hp zeolt X ,zeolt Y mordenit .

( Tnh theo mol cht phn ng Al203)
Zeolt
X
Y
Mordenit

Na20
3,6
8,0
6,3

Si02
3,0
20
27

H20
144
320
61

T ,0C
100
100
100

T(h)
7
7
168

Si02/Al203
2,5
5,0
12

I.4.2 Tng hp zeolt t khong st t nhin .

Ngoi hng tng hp zeolt i t ngun Si v Al ring l tr thnh ph bin, mt hng
nghin cu mi cc mt s nh khoa hc quan tm , l tng hp zeolt t khong st t
nhin .t bit l khong st m y l cao lanh .
Thnh phn ho hc ca cao lanh .
y l mt khong st t nhin ngm nc m thnh phn chnh l kaolint , c cng thc ho
hc n gin l .
Al203.2.Si02.2H20 .
Cng thc l tng l :
Vi hm lng

Al4(Si4010).(0H)8 .
: Si02 = 46,54 .
Al203 = 39,5%.
v H20 = 13,96% .

Tuy nhin trong thin thnh phn l tng ny rt him [ 4 ].trong cao lanh ngoi 3 thnh phn
chnh k trn thng xuyn c mt Fe203 , Ti02 , Mg0 , v Ca0 ,ngoi ra cn c K20 , Na20 vi hm
lng nh v cc khong khc nhau : feldspar , limonit , quartz , anatase .
So vi cc khong khc , lng Al203 trong caolinite thng ln hn t
(36,83 40,32),% cn lng nc hp ph trn b mt , lng K 203v Mg0 thng rt nh ,
tng ng khng vt qu 2% ,1% v 1,2% [4] .
Thnh phn ho hc ca kaolinit c nh hng ti cu trc tnh cht v kh nng s dng chng
. Do , vic xc ng chnh xc thnh phn ho hc ca kaolinit l rt cn thit, nhm nh hng
bin tnh chng theo cc mc ch s dng khc nhau sao cho em n hiu qu nht .
Phng php tng hp zeolt i t khong st .
Qua nhiu cng trnh nghin cu th khong st t nhin c s dng lm nguyn liu ban
u c ngun ngc xut s v thnh phn ho hc rt khc nhau . Quy trnh tng hp t mi loi c
khc bit ng k . Tuy nhin, u ng ch ca phng php ny l cc khong st u c
nung nhit cao ( 650 700)0C nhm loi nc cu trc trc khi to thnh cc aluminosilicat
tinh th .
I.5 Tnh cht xc tc ca zeolt .

30

Cc zeolt c ng dng rng ri lm xc tc cho nhiu qu trnh chuyn ho hc nh c 4

tnh cht c trng sau [ 21 ] .
Zeolt c kh nng trao i ion : nh tnh cht ny m ngi ta c th a vo trong cu trc
ca zeolit cc cation c tng cht xc tc nh : Cu ,Co,Fe,Mn, cho phn ng oxy ho hay trao
i vi cc cation chuyn sang dng H+ cho cc phn ng cn xc tc axt.
Cc zeolt sau khi trao i vi ion H+ tr thnh axt rn v cha nhiu tm axt v lng axt
tng ng , c kh nng xc tc kh ln cho qu trnh chuyn ho hc .
Th tch xp trong cc zeolt rt ln , cho php chng hp ph mt lng ln cc cht phn
ng . Nh vy , nng cc phn t xung quanh tm hot tnh s ln hn b mt ngoi ,kh
nng tng tc phn ng cao hn , c bit cho phn ng lng phn t nh Craking, Olygome
ho , chuyn dch hyderua .
Vi h cu trc mao qun ng nht, ng knh nh hn 10A0, cc zeolt th hin tnh chn
lc rt cao .Qu trnh khuch tn cc tc nhn phn ng v cc sn phm trong l xp ca zeolt
ng vai tr quan trng trong phn ng xc tc v nh vy s nh hng n tc phn ng cng
nh vic phn b sn phm .
Trong 4 tnh cht ny ,2 yu t chim v tr quan trng nht , nh hng chnh n hot tnh xc
tc chnh l tnh cht axt b mt v kh nng chn lc hnh hc ca zeolt . y cng chnh l iu
kin c bn trong la chon xc tc thch hp cho tng qu trnh phn ng nhm t hiu qu cao
nht.
I.5.1Tnh cht xc tc b mt .
I.5.1.1.Khi nim v s hnh thnh cc tm axt trong xc tc .
Khi nim v axt b mt ca xc tc rn xc pht t qu trnh quan xc thc nghim t cc
cng trnh trc . Mt s phn ng c xc tc bi cht rn cho cc sn phm gn ging qu trnh
s dng cc axt thng thng .Cc nh khoa hc tha nhn rng cc tnh cht ca nhiu xc tc
ch yu l cc zeolt chnh l ngun gc hot tnh xc tc ca chng trong cc phn ng gy ra theo
c ch cacbocation nh crackinh , polyme ho , izome ho , alkyl ho [33].
Tnh cht ca zeolt thc hin bt ngun t c im cu trc c bit v thnh phn ho hc
ca n . Mi t din Al0 4 hoc Fe04 mang mt in tch m c trung ha bng mt cation kim lo
ho tr 1 ,thng l Na hoc cao hn . khi thay th ion Na bng cc cation khc s lm xut hin
proton trong zeolt
Trong zeolt c hai loi tm axt : Mt c kh nng cho proton (tm axt Bronsted). Mt loi c
kh nng nhn cp electron ( tm axt Lewis) .cc tm ny c hnh thnh t nhiu kiu khc nhau
.
S hnh thnh tm axit Bronsted:

30

- Cc nhm ( OH) tn ti trong cu trc zeolite l do sau khi trao i cation v phn hu
nhit hoc do phn ly cc phn t H2O bi trng tnh in ca cc cation trao i a ho tr [ 7 ] .

30

+
O
R NH 3

Al

Si
O

O
Al

O
Si

R -N H 2

n+

M (H 2 O)m
O

Al
O

O
Si

..
O

Al
O

O
-

Si
O

H 2O

Al
O

M (H 2 O)
m -1
..
O
O
-

Si
O

-1 +

Al
O

O
Si

- Tm axit Bronsted hnh thnh t qu trnh x l zeolite trong mi trng axit, i vi cc

zeolite c t s SiO2 /Al2O3 cao, c nng thp ( 0,05 N)
Na+-Z + HCl H-Z + NaCl
- S trao i cation ca zeolite vi cc cation a ho tr (nh cc kim loi kim th, t him,
kim loi qu) cng lm xut hin dng proton ho M n+HZ. Cc cation ny c trao i di dng
phn t ngm nc Mem+(H2O)x. Nh tc dng ion ho ca cu trc zeolite, dng phn t ngm
nc s chuyn thnh dng [Mem-1(OH)2]H+ lm xut hin proton. S bin i ny c th c biu
din nh sau: [7]

30

3+

2+

La (H 2 O)
x
O

(a) La (OH )

Al
O

O
Si

Al
O

Al

Si
O

H
O

Si

Si
O

Al

OH /A l = 1/3

H
+

(b ) La (OH )2
O

Si

Si
O

Al
O

(c) La

O
Si

O
5
2

Al
O

La

O
-

Al
O

H
O

Si

Al
O

O
Si
O

Lc axit ca tm axit Bronsted ph thuc vo nhiu yu t nh: thnh phn ho hc (c bit l

t s SiO2/Al2O3), cu trc ca tinh th zeolite. Lc axit tng khi t s SiO2/Al2O3 tng. Lc axit
cng thay i khi thay i cc cation b tr in tch. Lc axit ca cc tm axit l khc nhau ph
thuc vo s phn b cc tm Al gia cc tm Si.
S hnh thnh cc tm axit Lewis .
Ngoi tm axit Bronsted, zeolite cn c cc tm axit Lewis. S hnh thnh tm axit Lewis l do
tn ti Al trong mng cu trc. Khi nguyn t oxy b tch ra, nhit cao, khi lin kt vi Al th
s xut hin tm axit Lewis.[4]

Tm Bronsted

Tm

H+
O

Si

Al

Si

Al

Si

Al

Trong mng cu trc ca zeolite lun tn ti tm axit Bronsted, nhng i

OO

OO

OO

H2O

vi loi tm axit Lewis th ch xut hin sau khi x l nhit. i vi mt s loi zeolite, mng
cu trc khng phi hon ton cha tm axit Lewis sau khi x l nhit. Bi v, sau khi tch H 2O
hon ton khi mng cu trc, mng cu trc s b sp hon ton, c bit cng d sp mng i vi
cc zeolite c t s SiO2/Al2O3 cng thp.
I.5.12 S chn lc hnh dng ca Zeolt.

30

V nguyn tc, mt phn t mun phn ng trong cc Zeolt X,Y,P)cn phi tri qua cc
giai on sau .[21]
-

Hp ph trn b mt xc tc.

Khuch tn qua cc ca s vo mao qun v tin v pha tm hot tnh.p

Hp th trn cc tm hot tnh bn trong mao v to hp cht trung gian ca phn ng .

Phn ng

Gii hp ph v khuch tn ra khi mao qun. Qua cc giao on ny c th nhn thy kh

nng khuch tn phn t c nh hng rt ln n ton b tin trnh phn ng. M kh nng khuch
tn va ph thuc vo bn cht phn t li va ph thuc vo kch thc ca h mao qun trong
Zeolt, do tnh chn lc hnh hc ca Zeolt quyt nh. Vi cu trc cc mao qun c bit v rt
ng u, Zeolt ch cho php cc phn t c kch thc nh hn ca s vo v thot ra khi cc
mao qun ca n. Chnh v vy cc hin ng chn lc hnh dng trong mao qun ng vai tr quan
trng hn b mt ngoi ht. Ngui ta phn bit ba loI chn lc hnh dng khc nhau.
1. Chn lc hnh dng i vi cc cht tham gia phn ng.
2. Chn lc cc trng thi trung gian.
3. Chn lc cc sn phm to thnh .
*Chn lc cc cht phn ng.
Cc tm xc tc nm trong cc khoang hoc mao qun c ng vo b gii hn bi kch
thc ca s. Nh vy ch c cc cht phn ng c kch thc nh hn hoc gn bng ng knh
cc ca s ny mi c th khuych tn trong cc mao qun n cc tm hot ng v tham gia
phn ng.

V d : Phn ng Cracking n-Ocxan.

Hnh12: Chn lc cc cht phn ng.

30

* Chn lc cc trng thi trung gian ca phn ng ln so vi ng knh cc mao qun th

phn ng khng th xy ra ngay c kh cc cht phn ng v sn phm mong mun c th khuych
tn d dng ra ngoi cI l xp c th ly phn ng phn b li hydrocacbon ca toluen lm v d
sau.

Hnh 12 chn lc sn phm to thnh

Ch c cc sn phm phn ng c kch thc nh hn cc mao qun mi c th khuych
tn ra ngoi cc l xp di dng cac sn phm cui cng. Cc sn phm cng knh khc, nu c
to thnh trong qu trnh phn ng, s bin i thnh cc phn t nh hn hoc ngng t li bm
cht vo cc mao qun lm mt hot tnh xc tc.
Loi chn lc ny rt thch hp cho nhng phn ng cn chn sn phm mong mun trong s
ng phn ca n.V d chn lc dng Para trong phn ng alkyl ho toluen. S to thnh ba ng
phn octo,meta, para do kh nng khuch tn ra ngoi mao qun quyt nh. Trong s 3 ng phn
ny dng para khuch tn gn 1000 ln so vi hai dng kia. Do s hnh thnh dng para trong
mao qun cng ln hn octo v meta nhiu ln.
I.5.2 V tr ca cc Cation trong Zeolt. [30]
Cc tnh cht ho l ca zeolt k c tnh cht xc tc ph thuc rt nhiu vo bn cht v v
tr ca cc cation .
Qu trnh trao i cation ban u nh Na +, K+ bng cc cation n ho tr, a ho tr, hoc
bng ion H+. Tc trao i khong t 0% n 80% lng cation xy ra Iu kin bnh thng v
tc trao i tng i nhanh v tr nhng cation v tr rt kh v thng phi qua qu trnh
x l nhit v thi gian, nguyn nhn l do s phn b cc cation cn li nm su trong cc mao
qun nh .
i vi Zeolt X, Zeolt Y, V tr cation c xc nh nh trn hnh sau:

30

Hnh 14 V tr cation: S1, SI, SII, SII , SIII trong Zeolt X, Zeolt Y.
V tr SI nm ti tm ca lng tr 6 cnh bi 6 cu ni oxy, c 6 mng c s.
V tr SI nm trong Sodalt trn mt bn khc ca mt 6 cnh so vi v tr SI
V tr SII c b tr khng nm trn mt 6 cnh trong lng Sodalt m nm bn ngoi mt 6
cation tt c v tr ny u l Na +.

cnh trong l xp ln. C 32 v tr S II trn mt c s. Cc

V tr SII nm trn mt bn ca khung Zeolt, khng trn mt 6 cnh, v n c xem nm trong

khong ca Zeolt.
V tr SIII nm trong ming l xp, v tr ny c xem nh l gng ca v tr S II. C 48 v
tr Cation SIII, s chim c ca cation trong nhng v tr ny khng tun theo quy lut.
Khi Zeolt dng Hydrat th tt c cac cation c b tr cc v tr S I, SI trong lng chnh
c Sovat ho bi phn t nc(H 2O). Khi loi nc ra khi cu trc th v tr caction b chuyn
di v c t thay i v c thng s trong cu trc Zeclt
V tr Caction SII v SIII nm trong l xp ln nn kh nng trao i caction l d nht. V tr S I
v SII nm trong t xp b (trong sodalit) nn kh nng trao i Caction c kh hn. Cn i vi
v tr Caction SI nm trong lng tr 6 cnh th ch nhng caction kh nc mi chu lt vo bn
trong thay th. S phn b Caction trao i c th biu din nh sau:

SII , SIII

H 2O

H 2O

SI, SII

+ H2O

SI

+ H2O

Loi chn lc ny rt thch hp cho nhng phn ng cn chn sn phm mong mun trong s
ng phn ca n.V d chn lc dng Para trong phn ng alxyly ho toluen. S to thnh ba ng
phn octo,meta, para do kh nng khuch tn ra ngoi mao qun quyt nh. Trong s 3 ng phn
ny dng para khuch tn gn 1000 ln so vi hai dng kia. Do s hnh thnh dng para trong
mao qun cng ln hn octo v meta nhiu ln.
I.5.3.Trao i ion trong Zeolt.
I.5.3.1 Tnh cht trao i ion trong Zeolt.
Zeolt c kh nng trao i ion. Nh tnh cht ny m ngi ta c th da vo cu trc ca
Zeolt cc Cation c tnh cht xc tc nh Cation kim loi kim, kim loi chuyn tip Nguyn tc
l da trn hin tng trao i ion thun nghch hp thc gia cc Cation trong dung dch vi cc

30

Cation trong thnh phn ca Zeolt. S trao i tng ng 1-1 theo ho tr, Trong Zeolt
Cation trao i l Cation b tr in tch h.
Khi cho Zeolt tip xc vi dung dch cht in ly. V d CaCl2 th xy ra chu trnh trao i
l:
2Z Na + Ca2+(dd)

2Z Ca + 2Na+

Cc Cation nh Ca2+, i Na+ gi l cc Cation i, chng c kh nng trao i ln nhau v sau

mt thi gian nht nh, qu trnh trao i t trng thi cn bng Cng nh i vi i khong st,
kh nng trao i Zeolt ni chung cng c c trng bng dung lng trao i Cation. i vi
mt s Zeolt chng hn nh MeZSM -5, dung lng trao i lin quan trc tip n hm lng Me
c trong thnh phn cu trc. Do , m t dung dch trao i Cation ta c th xc nh c hm
lng trao i Me c trong mng li c trc ZSM5. [4]
Do cu trc tinh th trong khng gian 3 chiu bn vng nn khi trao i ion cc thng s
mng ca Zeolt khng h thay i , khung Zeolt khng b trng n . y l c tnh qu gi m
nha trao i ion v cc cht trao i v c khc khng c c.
Khi xy ra qu trnh trao i Cation th ng knh trung bnh trong cc mao qun ca
Zeolt tng ln chng hn nh mt Cation Ca 2+ s i c & Cation Na+, 1La3+, th s Cation s
bt i v vy ng knh trung bnh ca mao qun tng ln. Hoc l khi 1H + s trao i c vi
1Na+ th tnh axit ca Zeolt khng nhng tng m ng knh trung bnh ca mao qun cng tng
theo v kch thc ca nguyn t H nh hn kch thc nguyn t Na.
Qu trnh trao i ion ph thuc vo nhiu yu t nhng ch yu l ph thuc vo 6 yu t
sau y.
-

Bn cht ca Cation trao i :in tch ,kch thc.

Nhit mi trng phn ng .

Nng cation trong dung dch.

Bn cht ca anion kt hp vi cation trong dung dch.

Dung mi ho tan (thng thng l dung mi nc).

c im cu trc ca zeolt.

S trao i cation trong zeolt c thc hin nh cc ca s mao qun c nh hng rt ln

n dung lng trao i ion.

30

Bng 5 Trnh by dung lng trao i cation ca mt s Zeolt ph thuc vo kch thc mao
qun v t s mo SiO2/Al2O3.

Tn zeolt

Kch thc mao qun

A0

T l s mol

Mldl
Na+/1gmu
7,0

4A

4,2 v 2,2

SiO2Al2O3
2

7,4

2,5

6,4

7,4

4,4

Chabazit

3,7 x 4,2

4,9

Kromit

3,6 x 5,2

3,8

Mordent

6,7 x 7,0

10

2,6

Bn cnh dung lng trao i vn tc trao i cation cng ph thuc vo ng knh mao
qun v kch thc ca cc Cation. Vn tc trao i l khi kch thc Cation b v v ng knh
mao qun ln. Khi Cation c kch thc ln hn ng knh mao qun th s trao i c th din ra
chm trn b mt zeolt.
Qu trnh trao i Cation ca zeolt c th c din theo phng trnh sau[17].

ZA.BZ B (Z) + ZBAZ A (S) ZA .BZ B (S) +ZBAZ A (Z)

Trong :
ZA, ZB ln lt l din tch ca Cation trao i A,B
(Z), (S) l ch s ca Cation trong zeolt v dung lng tng ng
S trao i Cation dn n s thay i bn , tnh cht hp th chn lc hot tnh xc tc v
cc tnh cht quan trng khc.
I.5.3.2.Kh nng trao i ca Cation trong zeolt .
hiu r qu trnh trao i ion cn xt c th cc chi tit trong mt s trng hp sau y.
trng thi tinh th ca zeolt th cc cation dng nm trong tinh th zeolt c n b bi
nhng in tch m d tha ca cc ion m [SiO4]4 hoc ion m [AlO4]5 gy ra.
Do kh nng ny nn zeolt c kh nng trao i ion mt cch d dng khi zeolt tip xc
vi mt cht trao i ion c th no .
i vi mt s zeolt tng hp thng d dng trao i mt s lng ln cc cation khc
nhau nh Li+; K+; Te+; Ca2+; Sr2+; Ba2+; Mg2+; Zn2+; Pb2+; Ni2+;Co2+ CH3NH3+; C2H5NH+3;
nC3H2NH3+; n-C4H9NH3+; n- C6H13NH3+; CH3(C2H4)4 CH(CH3) NH3+; (C2H5)4N+..
Nhng zeolt cng xp cu trc cng h cng d trao i ion hn . Chng hn nh fozazit,
Chabazit, mordenit, trao i ion d dng hn . Loi c cu trc st hoc c kh trao i ion hn
nh Anacim.

30

Sau y l mt s kt qu nghin cu v kh nng trao i ion gim theo chiu dy Zn > Ba >
Sr > Ca > Co > Ni > Cd >Hg > Mg
Khi trao i ion vi nhng cation kch thc ln hiu ng sng lc phn t ca zeolt rt r qua
vn tc trao i ion ca cc cation. Vn tc trao i ion ca cc cation c kch thc ln hn b
gim ng k so vi ion c kch thc b. Vi cc ion cht hu c tng i cng knh , linh
trong ion rt b nn mc trao i ion gim t 92% v 23% ng vi kh nng trao i ca ion
NH+4 v (CH3)4N+.
Trong qu trnh trao i ion, cu trc ca zeolt b thay i t dng zeolt Na sang dng
zeolt H khng c trng hp no gi nguyn vn. V d vic trao i ion Na + loi zeolt A bng
cc cation NH+4 , Ba2+, Zn2+, Co2+ ,c th dn n vic ph v hon ton cu trc tinh th ca zeolt.
Khi trao i ion hu c, mc trao i gim r rt khi chiu di ca mt xch ca cation
hu c tng ln ngay c s phn nhnh ca cc cation hp cht hu c cng lm gim mc trao
i ion.
Ring zeolt X kh nng trao i cation c kch thc nh cng nh ln hon ton xy ra trong
vi pht v chng c cu trc rt m. Kh nng trao i cation ca cc mng li aluminosilicat
trong cc zeolt tng theo dy.
Anacim < Mordenit < Sabazit < Fozazit.
Tnh ton so snh kch thc ca l v ca cation trao i trong cu trc c th ch ra mc
trao i ca tng loi zeolt. Nhng thc t ca gi tr ny thng nh hn gi tr tnh ton v chng
cn chu nh hng nng lng b mt ca zeolt.
Da trn c s ca cu trc v kh nng tnh ton cho thy khi thay i ion Na + trong zeolt A
bng ion Ca2+ trong dung dch l khng th xy ra s trao i hon ton . V vic trao i khng
nhng lm thay i dung lng hp ph m cn thay i kh nng chui vo cc rnh khoang trong
zeolt ca cc phn t khc nhau. S thay i ion khng thay i cu trc tinh th zeolt nhng
trong nhiu trng hp lm kch thc hiu dng ca l b thay i. V d khi hay th Na + bng
Ca2+ trong zelt th ng knh hiu dng ca l b gim .
S thay i v tr cation trong cu trc tinh th zeolt c ngha c bit l khi thay i cation
ho tr 2. V vy v tr cation ho tr 1 v ho tr 2 l khng ging nhau.
Vic tch cc cation ra khi mng li tinh th thng tin hnh bng cch trao i ion [6]
V d: Vic tch Na+ ra khi zeolt ta lm nh sau:
Cho zeolt c cha Na+ trong tinh th tip xc vi dung dch NH +4 ri to iu kin thch hp
Na + ra khi tinh th zeolt v NH+4 vo tinh th thay th ion Na+.

30

Bc tip theo l thu li zeolt c cha NH+4 thay th cho ion Na+ trn bng cch nung nng
trong iu kin thch hp c xy ra s phn hu ca NH+4.
Phn ng phn hu NH+4 l:
NH4+

NH3 + H+ ( li zeolt)

Khi ion H+ c trong zeolt nhit cao chng kt hp vi oxy v tch khi b mt ca zeolt
di dng phn t nc. Do vy cc tm axt lewis trn b mt zeolt c hnh thnh to nn hot
tnh c bit cho zeolt . Loi zeolt Zeolt sau khi s l cation n nh ngi ta ch nhn c t
zeoltY vi t s SiO2/Al2O3 cao cn zeoltX ngho SiO2 hn khi kh cation mc cao khng n
nh.
Nhn chung s trao i ion gia cation Na + v ion Men+ xy ra mc khc nhau khi Me n+ l
khc nhau ng thi nng dung dch khc nhau, nhit khc nhau, mc trao i cng khc
nhau .
I.5.3.3 Tnh cht chn la v sng lc ion.
Tinh th zeolt c nhiu rnh, khoang nn din tch b mt zeolt rt ln so vi cht khc nhau
cng th tch, b mt zeolt khong 800-1000m2/g [23]
Din tch b mt ca bt c mt n v th tch no ca zeolt u bao gm din tch b mt
bn ngoi v din tch tng th cc b mt trong cc rnh khoang. B mt rnh khoang rt ln li c
tnh cht c bit do cu to tinh th zeolt to nn do vy chim vai tr ch yu trong kh nng trao
i ion v hp th .Nhng cc cht mun tip xc vi b mt bn trong phi i qua cc ca s
ca zeolt. Cc ca s to vng bi oxy kch thc b tp trung nhiu, nguyn nhn t oxy gy nn
tnh cht sng lc ion phn t cho zeolt.
trong zeoltX: bn knh ion ca N(CH 3)+4 cn nh hn bn knh ca s nn xy ra s trao i
ion qua l zeolt X, cn N(C2H5)4+ bn knh nh ln hn bn knh l ca s th khng trao i c
qua l ca zeolt X.
Nhiu cng trnh nghin cu cho bit cc ion khc nhau i vi mt zeolt cng c s chn
lc khc nhau hoc cng mt s ion th s la chn trn cc zeolt khc nhau l khc nhau. Ngi ta
chn kim loi kim vi zeolt X v zeolt Y minh ho iu ny
Zeolt X th t u tin la chn, sng lc gim theo dy sau
Na+ > K+ >Rb+ > C+S > Li+ [23]
Zeolt Y s la chn sng lc cc ion kim loi kim gim theo th t u tin sau:
C+S > Rb+ > K+ > Na+ > Li+ [23]
Tm li s sng lc ion ca zeolt ph thuc vo nhiu yu t nh bn cht ion bn cht
zeolt nhit dung mi. Do , khi nghin cu kh nng trao i ion kh nng hp th ca zeolt
no cn phi bit r tnh cht ca zeolt dung dch ca cht tan v cc yu t lin quan khc.

30

I.5.4 Mt s tnh cht khc.

*Tnh n nh nhit .
Bng phng php phn tch nhit, ngi ta nhn thy s tc ng ca nhit vo zeolt . i
vi mt s zeolt bt k th khi nhit tng ln th chng b mt nc bin i cu trc tinh th v
cui cng dn n s ph v cu trc tinh th. Cc zeolt khc nhau, chu nh hng nhit khc
nhau. [6]
Trong qu trnh s dng cc zeolt nghin cu khi gia c nhit cn thit phi nm chc
tnh cht ny khng gy nh hng n kt qu
*Tnh n nh axit
bn ca zeolt i vi axit thng rt km. Khi zeolt tip xc vi axt thng xy ra s bin
i cu trc tinh th. Cc loi zeolt khc nhau kh nng bn vng trong cc loi axt khc nhau l
khc nhau.
* Tnh n nh trong dung dch kim.
Dung dch kim c nng OH- khc nhau thng gy nn mc nh hng khc nhau cho
zeolt. Khi tip xc vi nng long ca dung dch kim cao dn n qu trnh ho tan tinh th
zeolt.
V d: zeolt A ngm lu trong dung dch NaOH c th b ho tan
Nhn chung nhiu zeolt khng bn trong mi trng kim, PH ca dung dch kim quyt
nh vic ho tan hay hnh thnh sn phm [23]
* bn vng ca cu trc zeolt vi phng x.
Ko dI thi gian chiu mt lng Ntron cao vo zeolt ngi ta nhn thy zeolt c kh nng
ngn cn bc x m khng lm nguy him cu trc ca n.
Mt lng ln tia c chiu vo zeolt ngi ta nhn thy s

nh hng gy

ra cho mng li zeolt l khng ng k [23]

I.6 ng dng ca zeolt.
I.6.1 ng dng ca zeolt trong tng hp hu c
*Abkyl ho hp cht thm [9]
_ R + CH2 = CH Xuctac

R

_ CH CH3
R

Zeolt c s dng l : zeolt Y, X, Mordent, Omega, Zeolt ZSM-5, Zeolt ZSM-8 p sut
kh quyn nhit 2000C, hiu sut t c 26,5%.

phn chia Toluen [9]

30

2C6H5- CH3

C6H6 + C6H4CH3

Nhit tin hnh phn ng khong(250 3500C)

Xc tc l cc Zeolt; Fozazits; zeolt Y; zeolt HZSM-5 Vi cc bin tnh : 0,65 MnNaY, 0,65
NdNaY chuyn ho c th t ti 43%

Alkyl ho parafin bng olefin [9]

CnH2n + 2 + CmH2m

t0
Cm+nH2(m+n)+2
Xt

Xc tc Zeolt Y vi cc cation La, Ca, nh CaLaHY hiu sut

Sn phm c th t rt cao (hiu sut sn phm t ti 76%, nhit phn ng 1000C) p sut
2Mpa.

Amin ho Butanol bng amoniac [9]

6C4H9OH + 3NH3

t0
C4H9NH2 + (C4H9)2NH + (C4H9)3N + 6 H2O.
Xt

Phn ng xy ra iu kin p sut kh quyn, nhit tng ng 250 0C 4500C. Xc tc

Zeolt c xp cao: NaY, NaX hiu sut Amoni ho c th t 72,8%.

Mt s ng dng khc trong tng hp hu c.

+ Thu phn axetylen.

CH CH + H2O

t CH3CHO

Xc tc Zeolt c tm H+ [9].
+ Trng hp Vinyl ste .
0

nH2C = CHOR t

[- CH2-CHCOR-]n

Xc tc l zeolt, Fozazits, Mordent [9]

+ Hydro ho Olefin [9]
t0
R- CH= CH2 + H2 Xt RCH2CH3
Xc tc l zeolt l Na-Mordent, ZeoltNaA.
+ Hydro ho thm hp cht vng 6 cnh [9].
- CH3

t0
Xt C6H5 + 3H2

Xc tc l zeolt Nax, NaY, NaA, CaY, HY, NdY.

I.6.2 ng dng ca zeolt trong cng ngh ho hc du [1,3,7]
Zeolt l xc tc cc k quan trng trong cng nghip lc ho du do nhng u im sau:
+ Zeolt c b mt rig ln do c kh nng hp th cao, tnh hp th ca zeolt c th
c khng ch v thay i tu thuc vo tnh a nc hay k nc ca vt liu.

30

+ c th iu chnh c lc axit v nng tm axit trong zeolt cho ph hp vi tng

phn ng c th.
+Kch thc ca cc mao qun ca zeolt ph hp vi nhiu phn t c kch c t 5A 0 n
12A0. Mt khc trong zeolt tn ti in trng mch nn cc phn t tham gia phn ng c hot
ho trong mao qun tc phn ng s nhanh.
+ Mt khc nh ni trn l zeolt c tnh chn lc nguyn liu c ch sn phm , zeolt
c tnh bn nhit v thu nhit tt
V vy zeolt c ng dng nhiu trong cng ngh lc - Ho Du

Zeolt trong phn ng Crackinh xc tc.

Crackinh xc tc tng si FCC l cng ngh s dng xc tc ln nht. Zeolt lm xc tc cho

cc phn ng sau:
0

CmH2m+2 t
CnH2n

CmH2m+2 + CpH2p

t0
CmH2m + CpH2p
Xt

t0
C6H5C2H5
C6H6 + C2H6 + C2H6
Xt
t0
Xycloprafin CuH2n
CmH2m + CpH2P
Xt
Xc tc thng l Zeolt Y siu bn nhit (USY) kch thc l xp ln cc phn t chui
qua v xy ra phn ng ngoi ra cn c th dng cc xc tc ZeoltX, ZSM-5, ZSM-11, Xc tc trn
c s Zeolt c u im l gi thnh thp d ti sinh v cc ch bm trn b mt ch khng bm vo
trong cc mao qun.

Zeolt trong qu trnh alkyl ho

Xc tc thng s dng l xc tc cha Zeolt loi CaNiY, LaHY nht l ZeoltY cha Canxi v
nguyn t t him
Vi u im l sn phm tinh khit cao chn lc ln. Ngoi ra cn c th dng HZSM-5 bin
tnh, ZSM 12.

Zeolt trong qu trnh izome ho

Vi qu trnh izome ho phn ng tin hnh tt s dng ph bin lm xc tc lng chc

nng, Pt ng vai tr chc nng oxy ho kh Zeolt ng vai tr chc nng axit. Zeolt c s
dng ZSM-5, mordenit, SAPO 11. Xc tc trn dng iu ch MTBE

Zeolt trong phn ng thm ho olefin.

30

Mc ch l t cc hydrocacbon mch thng to thnh cc hydro cacbon thm l cu t c ga

tr s octan cao trong nguyn liu xng, nguyn liu btx s dng rng ri trong tng hp hu c.
xc tc s dng l HZSM 5, GaHZSM 5.

Zeolt cho qu trnh Hydrocracking.

Qu trnh ny gm 2 phn ng: Cracking v phn ng xy ho, cha oxy ho kh c tc dng

tng tc phn ng hydro ho - de hydro ho. Mt s loi xc tc s dng nh sau: ZSM 5
(Fe)ZSM-5, Sapo 5, PtY, PdY.
Mt s phn ng chnh:
RH + H2

t0
R1H + R2H
Xt

R-

t0
Xt

+H2

R H

I.6.3 ng dng Zeolt trong bo v mi trng.

X l kh thi:

S dng xc tc CuZSM-5, hoc Zeolt trong b 3 lp acht thi c hi v dng khng

c: CO2, NO2, ngoi ra cn c Zeolt Y cng mt s nguyn t t him: Co, La, Nd mang trn
Zeolt cng c kh ngng x l cht thi.
X l nc thi:
Do b mt ring ln ca cc Zeolt t nhin nh Mordenit, Clenoptilonit nn kh nng gi
bn ca Zeolt l ln, Clenoptilonit c th lc khng nhng ht huyn ph ln m c ht keo c
ngun gc V c v hu c- Clenoptilonit c th lc c nc c c cao 30 70 mg/l hoc
c th ti 52mg/l. Ngoi ra cn c th lc vi khun.

X l cc kim loi trong nc.

Da vo c im ca Zeolt c kh nng trao i ion ngi ta s dng Zeolt vo t nhin v

Zeolt tng hp x l cc Cation c hi trong nc nh NH 4+, Cu2+, Pb2+ v trong Zeolt tng
hp thng c cha cc kim loi kim (v d Na+) d b tch ra ngoi theo phn ng:
NanZ + mNH3+

(NH3)nZ + nNA+ + ( m - n) NH4+

( Vi n<m, m, n l cc s cation).
Ngi ta s dng Zeolt tng hp Na, Zeolt t nhin Moredenit Clenoptilonit
Chng II
Gii thiu v phn ng Crackinh xc tc.
II.1 S lc v khi nim phn ng Cracking xc tc.
II.1.1 S lc v qa trnh Cracking.

30

Qu trnh Cracking xc tc c nghin cu t cui th k th 19 nhng mi n nm

1923 mt k s ngi php tn l Houdry mi ngh a qu Process Corporation. Cho n ngy
nay, hn su mi nm pht trin qu trnh ny cng c ci tin v hon thin nhm mc ch
nhn nhiu xng hn vi cht lng xng ngy cng cao hn. ng thi ngoi mc ch nhn xng
ngi ta cn nhn c c nguyn liu v cht lng tt cho cng ngh tng hp ho du v ho
hc [3]
Nguyn tc ca qu trnh Cracking xc tc c th m t bng s khi sau.
Nguyn liu

Chun b

L phn ng

x l

Xc tc
lm

Sn phm qua chng tch

Xc tc
ti sinh

vic
Qu trnh Cracking xc tc l mt qu trnh khng th thiu c trong bt k nh my ch bin
du no trn th gii v qu trnh ny l mt trong nhng qu trnh chnh sn xut xng c tr s
octan cao.
II.1.2 Khi nim v qu trnh Cracking:
Cracking l mt qu trnh phn ct lin kt C-C ca hydrocacbon c khi lng phn t (KLPT)
cao to ra cc phn t c KLPT thp hn so vi gi tr ng dng tt hn. Cracking l mt qu trnh
thu nhit , v vy xy ra thun li nhit cao.
Phn ng Cracking c chia ra lm hai loi: Cracking nhit xy ra theo c ch t do di
tc dng ca nhit v Cracking xc tc xy ra theo c ch cacboncation nh tc dng ca cht xc
tc.
Phn ng Cracking mt s hydrocacbon thng gp v cc sn phm tng ng c th c
vit di dng tng qut nh sau:
Parafin Olefin + paratin nh hn

CnH2n+2 CmH2m + CPH2P+2 .

n=m+p

(2.1)

n=m+p

(2.2)

Olefin Cc olefin nh hn

CnH2n CmH2m + CPH2P

_

Cycloparafin(naphtan): b m vng to olefin, sau olefin c th b Cracking tip to

cc olefin nh hn.
_

Alkyl thm : thng b dealkyl ho to hydrocacbon thm khng c nhm th v

deolefin
ArCnH2n+1 ArH + CnH2n

Ar l gc thm

(2.4)

I.2 C ch phn ng Cracking

Cho n nay c ch phn ng Cracking xc tc cc hydrocacbon c tha nhn rng ri bao
gm s to thnh cacboncation trung gian, xy ra trn cc tm axit ca xc tc. Cacboncation bao

30

gm ion cacbeni (nguyn t cc bon mang in tch dng c s phi tr ba trng thi lai ho Sp 2,
V d : CH+3;, CH3-CH3+ - CH3) v ion cacboni (nguyn t ccbon mang in tch dng c s phi
tr nm trong c mt lin kt ba, tm hai electron, v d :
CH+5, CH3-CH3+ - CH3 ) . Tu theo dng tn ti ca ion trung gian l cacbeni hay cacboni v c
ch ion cacboni [2].
II.2.1 C ch ion cacbeni.
C ch ion cacbeni c Greensteleder v cng s ra ln u tin ngay t nm 1949 [23] ,
da trn c s ho hc ion cacbeni v Whitimore v Church. C ch ny c xc nhn v pht
trin cho n nay. C ch ion cacbenibao gm ion trung gian l cacbeni c xem nh xy ra theo
kiu dy chuynbao gm cc giai on sau:
a)

Giai on khi mo: ion cacbeni cto thnh hoc t qu trnh proton ho mt olefin

trn tm Bronsted (HZ)

R1- CH = CH- R2 + HZ R1- CH1- CH+- R2+Z-

(2.5)

Hoc c th t s tch H- ca mt parafin trn tm BronSted hay tm Lewis (L).

R1 - CH2 - CH2 - R2 + H2 R1- CH2 - CH+ - R2 + H2 + Z-

(2,6)

R1 - CH2 - CH2 - R2 + L R1- CH2 - CH+ - R2 +LH-

(2,7)

Ion cacbeni c to ra c th tham gia vo cc qu trnh chuyn dch hydrua hoc cracking
trong giai on mch tip theo.
b)

Giai on pht trin mch.

_Chuyn dch hydrua (ti sp xp): to cc ion cacbeni bn hn so vi ion cacbeni ban u bao
gm chuyn dch hydrua lin phn t
R1-CH2-CH+-R2+R3-CH2- CH2- CH2- R4
R1-CH2- CH2-R2+R3-CH2- CH2-CH+-R4

(2.8)

hoc chuyn dch hydruani phn t qua s to thnh phn ng trung gian Cyclopropan proton
ho, V d
C-C+-C-C-C-C

C-C--------- C-C-C

C-C+-C-C-C (2.9)

Phc trung gian dng Cyclopropan proton ha do Brower ngh nm 1980 [24] v c xc
nhn sau .
- Cracking: ion cacbeni to ra t giai on (b) hoc t qu trnh chuyn dich hydrua b phn ct
lin kt C-C theo quy tc (t lin kt C-C v tr so vi nguyn t cacbon mang in tch
dng) to ra mt olefin v mt ion cacbeni mi :
R3 - CH2 - CH2 - CH+ - R4 Ct R3 - CH2+ + CH2 = CH - R4 (2.10)

30

Ion bc mt R3CH2+ km bn chng c th chuyn thnh cc ion cacbeni bc hai hoc bc ba

bn hn hoc c th nhn H- to ra paratin.
c)

Giai on ct mch: ion cacbeni nhng proton li cho tm xc tc chuyn thnh

olefin
R - CH2- CH+- CH3 +Z-

R - CH2- CH = CH2 + HZ (2.11)

Hoc nhn H- t mt cht cho (v d cc) chuyn thnh paratin

R - CH2- CH+- CH3 +H--

R - CH2- CH2 - CH3

(2.12)

Tc ca giai on chuyn dch hydrua v Cracking ph thuc nhiu vo bn nhit

dng ca cc ion cacbeni ban u v sn phm . bn ca cc ion cacbeni gim theo th t :
Bc ba > bc hai > bc mt > CH3+
II.2.2 C ch ion cacboni (cn gi l c ch proton ho n phn t

hay c ch Haag-

Dessau) [25]
C ch ion cacboni do Haag- Dessau ra vo nm 1984 da trn c s ho hc cacboncation
trong supeaxit ca olah. C ch ny bao gm ion trung gian l cacbonni c to ra t phn ng
proton ho mt paratin
CnH2n+2 + HZ [CnH2n+S]+ + Z-

(2,13)

Ion cacboni trn hoc b hydro ho to ion cacbeni

[CnH2n+3]+

[CnH2n+1]+ + H2

(2.14)

hoc b cracking to ra cc ion cacboni mi

[CnH2n+3]+

[CmH2m+1]+ +CPH2P+2

n = m +p (2.15)

Do paratin l hydrocacbon no, bn nn trong phn ng (2.13) cn mt cht cho proton c lc

axit mnh. S proton ho mt paratin xy ra bi s tn cng ca proton vo lin kt C-H hoc C-C.
Mc nh hng ca mi c ch k trn ph thuc vo iu kin phn ng , bn cht ca
cht phn ng v xc tc.
Hin nay c ch phn ng Cracking xc tc vn cn ang c nhiu nh nghin cu quan
tm vi mc ch lm r bn cht ca cc trng thi chuyn tip, s tng tc gia chng vi cc
tm hot ng ca xc tc nh gi mc can thip ca mi c ch vo qu trnh cracking trn
cc xc tc khc nhau. Cc tnh ton ho hc lng t v ang c s dng nh hng bn
cht ho hc ca cacbocation trung gian trong phn ng cracking xc tc [2]
II.3 Lch s pht trin ca xc tc cracking:
Ngay t nm 1919 1920 Vin s H.D.Zelihekuu(Lin X c) nghin cu xc tc AlCl 3
trn s th nghim nhn xng v ch cho php tin hnh iu kin cracking xc tc nhit
2000C 3000C. Loi xc tc ny b mt mt nhiu do to phc hydrocacbon kh nng tip xc
gia nguyn liu vi xc tc km, phn ng xy ra tc chm, sn phm khng t yu cu.

30

Chnh cc hn ch ny dn n khng m bo hiu qu kinh t nn khng p dng vo quy m

cng nghip.
Nm 1928 Vin s F. Gudry nghin cu s dng t st t nhin qua x l s b bng
axit lm xc tc cho qu trnh cracking vi nguyn liu phn on nng nhn phn on xng.
n nm 1930 xc tc ny c p`dng vo quy m cng nghip nhng kt qa xc tc ny cho
thy hot tnh ca n thp.
Vo nhng nm 1950 nghin cu s dng alminosilicat (ASC) tng hp trong cng nghip
c thnh phn ho hc: SiO2 Al2O3 H2O vi t l SiO2:: 75- 90%; Al2O3::10-24%, loi xc tc ny
c s dng rng ri trong mt thi gian di, c cng nhn l xc tc c hot tnh v
chn lc cao.
n nhng nm 1960 nghin cu v ch to loi xc tc Zeolt v aluminosilicat cha Zeolt.
M nm 1972 s dng 80% xc tc cha Zeolt trong qu trnh cracking. Vic a zeolt vo
cht xc tc cho qu trnh FCC t nm 1962 [28] l mt bc nhy vt trong tin trnh pht trin
ca lnh vc xc tc cracking. Cc Zeolt ln lt th nghim l ZeoltA, Zeolt X , ZeoltY. Trong
s , Zeolt Y c dng cho m by gi v l thnh phn chnh cha th thay th trong hu ht
cc xc tc cracking cng nghip. Xc tc cha zeolt c nhiu u im ni bc so vi cc h xc
tc c trc . Chng c hot tnh cao, thi gian s dng di, bn nhit v thu nhit tt,
hiu sut to xng cao, to kh v cc thp, [29].
Hin nay, xc tc cracking cha Zeolt vn ang c nghin cu c v l thuyt vn thc
nghim nhm mc ch lm r bn cht xc tc v l gii v ca tng hp phn trong xc tc [3]
Cc ci tin ang c thc hin mnh m xc tc FCC theo cc hng lm tng hot tnh,
chn lc sn phm mong mun tng bn c, bn xc tc, bin nhit v thu nhit, tng kh nng
chng ng c xc tc vi nhng hp cht cha lu hunh, nit, cc kim loi nng (Ni, V) chn t
l thch hp gia cc hp phn xc tc v ti u ho quy trnh iu ch, gim gi thnh sn phm
II.4 Nhng yu cu i vi xc tc trong qu trnh Cracking xc tc
Hot tnh xc tc phi cao.
Hot tnh xc tc cng cao s cho hiu sut xng cng ln khi s dng xc tc c hot tnh cao
th th tch vng phn ng yu cu khng cao lm vn c th m bo nng xut yu cu. Do vy,
hot tnh xc tc l yu cu quan trng nht i vi xc tc dng trong qu trnh Cracking
Hot tnh xc tc ph thuc vo thnh phn ho hc, cu trc xc tc v.v
chn lc xc tc phi cao
Xc tc cn c chon lc cao cho xng thu c c cht lng cao v hiu sut ln v
trong kh Cracking c nng ln cc huyrcacbon c cu trc nhnh.
n nh ca xc tc phi ln:

30

Xc tc phi gi c nhng t tnh ch yu ( hot tnh chn lc ca n sau thi gian lm

vic lu di)
Xc tc phi m bo bn c v bn nhit
Trong qu trnh lm vic xc tc c xt vi nhau v xc tc c xt vi thnh thit b lm cho xc
tc d b ph v lm tn tht p sut qua lp xc tc tng ln, lm mt mt xc tc. V vy xc tc
phi m bo v bn c.
Trong qu trnh lm vic nhit c th thay i khi nhit cao nu xc tc khng c bn
nhit th c th b bin i cu trc dn n lm gim cc tnh cht ca xc tc
Xc tc phi m bo thun nht v thnh phn, v cu trc, hnh dng, kch thc.
Khi kch thc khng ng u s to ra nhng vng phn lp v c tr lc khc nhau v do s
phn lp theo kch thc nn s ph v ch lm vic bnh thng ca thit b. Mt khc, khi kch
thc khng ng u l tng kh nng v vn dn n lm mt mt xc tc. Cu trc l xp khng
ng u lm gim b mt tip xc dn n lm gim hot tnh xc tc .
Xc tc phi bn vi cc cht ng c ca nhng hp cht nit, Lu hunh, cc kim loi
nng, ko di thi gian lm vic ca xc tc
Xc tcphi c kh nng ti sinh
y l yu cu quan trng trong qu trnh s dng xc tc
Xc tc phi c kh nng ti sinh tt th s nng cao c hiu qu v nng sut ca qu trnh,
lng tiu hao ca xc tc gim xung
Xc tc phi sn xut r tin.
Phn ln cc xc tc s dng trong qu trnh cracking u mang li cht lng v hiu qu
nh alumino slocat v nh hnh, Zeclt
Ngy nay cng vi s tin b v thnh tu khoa hc v nhng cht pht minh tm ra rt
nhiu loi khc nhau, m hin nay Zeclt l loi xc tc dng ph bin v c hiu qu cng nh cht
lng sn phm cao nht trong qu trnh Cracking.

II.5 Phn ng Cracking xc tc du m.

Nguyn nhn c bn cho phn ng cracking xc tc trong cng nghip

thng l cc phn

on kerosen ( khong nhit si 1802700c), gasoil chng ct kh quyn (2703600c) gasoil

chng ct chn khng (3505400c) v c phn on nng hn. Cc nhm sn phm chnh bao gm:
kh ( kh kh C1C2v LPG C3C4 ) Xng phn lng c nhit si cui khong cch 2000C) cc
sn phm nng hn gm du nh LCO (2003500C) V du nng HCO (>3500c); sn phm rn l

30

cc bm trn b mt xc tc thnh phn cc sn phm thay i trong mt khong rng v ph thuc

vo nhiu yu t nh bn cht nguyn liu, xc tc; cc iu kiu phn ng (nhit , p sut, tc
np nguyn liu, t l khi lng nguyn liu /xc tc ). Ngi ta mong mun cc sn phm
LCO, HCO chuyn ho tip thnh xng, ng thi li hn ch s cracking su to cc v kh qa
mc
Trong cracking xc tc, bn cnh phn ng ca qu trnh l s phn ct C-C, nhiu phn ng
th cp cng xy ra lm tng tnh phc tp ca thnh phn sn phm. l cc phn ng chuyn
dch Hydrua, chuyn v nhm Alkyl, ng phn ho, ng vng ho, thm ho, ngng t, Cc
phn ng ny cng thng xy ra theo c ch cacbocation trn cc tm axit c lc khc nhau ca
xc tc, c minh ho hnh

Nhiu phn ng th cp trn bao gm s chuyn dch hydrua ni hoc lin phn t. V th,
chuyn dch hydrua l mt trong nhng phn ng rt quan trng trong ton b qu trnh cracking.
i vi phn ng cracking du m, mc chuyn dch hydrua s dn m gim thnh phn sn
phm olefin; tng hiu sut to cc; to xng nhiu hn v to kh t hn; Tuy nhin xng c ch s
octan gim [26]. Mc tham gia ca phn ng chuyn dch hydrua thng c nh gi da vo
t s mol Paratin/sletin sn phm (p/o) hoc gi tr nghch o ca chng (o/p).
Cracking du m nh l mt qu trnh rt phc tp. V th, nghin cu cc vt l
thuyt cracking v kho st hot tnh ca mt s xc tc, ngi ta thng n gin ha bng cch
s dng cc phn ng m hnh l cracking mt hydrocacbon ring r. Cc hydrocacbon thng
dng cho mc ch ny l cumen, n-decan ;iso octan; n-heptan; n-hexan,n-pentan. V ngay c cc
hydro cc bon nh nh n-butan, isobutan, propan. Trong s n-hecxan va c ng knh ti hn
nh ( 4,3A0) khng b khng ch hnh dng bi hu ht mao qun ca cc loi Zeolt, li va c
kh nng phn ng cracking tng i d. Tc phn ng cracking ph thuc vo kh nng to
cacbocation ca hydrocacbon. Theo , tc cracking gim theo th t: olefin > paratin >
cycloparatin. Cc vng thm l h lin hp bn nn rt kh b cracking ( thng ch xy ra nhm
th). i vi cc hydro cacbon mch h, ca mch cacbon. Tc to cc tng theo th t nguyn
liu: Parafin < naphten < olefin < hydrocacbon thm; v ph thuc nhiu vo cu trc tnh cht axt
ca xc tc, bn cht ca nguyn liu ca nguyn liu v qu trnh crackinh .

30

Trong my thp k qua ,cng ngh v thit b crcking xc ci tin v pht trin khng
ngng.t thit b crcking tng c nh n tng di ng v sau n cracking xc tc tng si
(FCC ) mt qu trnh gn lin vi s ci tin v pht trin ca thit b cracking xc tc l mt tin
trnh nghin cu pht trin v p dng rt mnh m ca cht xc tc cracking.
II.6. Cc yu t nh hng n qu trnh
II.6.1 Yu t v xc tc Zeolt.
Qu trnh trao i Ion H+ ca NaZ khng phi hon ton. Do , lng Na phi cn mt lng
rt nh trong xc tc. Hm lng d ny c nh hng ti hiu qu qu trnh. Nh vy, tnh axt
ca zeolt quyt nh hot tnh cracking c c l do kt qu trao i ion H + vi Na+ hoc Mnn+vi
Na. Vic gim t 0,27% xung 0,02% Na2O trong mu th nhit phn ng c th gim 500C m
vn

chuyn

ho

30%[27]

T l Si02 /Al203 cng nh hng n qu trnh cracking n- Hecxan nu nh t l ny tng th

hm lng nhm gim, ko theo s gim s lng tm axt nhng ngc li lm tng lc axt, thut
li

cho

cc

phn

ng

chuyn

ho

hydrocacbon

trn

xc

tc

lng

chc.

II.6.2 Yu t nh hng qu trnh to cc

Nguyn liu:
yu t nguyn liu l rt quan trng trong qu trnh cracking xc tc, theo quy lut thng thng
th tng phn nh ca nguyn liu, hiu sut hydroccbon C 3, C4 v xng u tng ln, cn hiu sut
l cc hp cht hydro va cc gim xung v ngc li cc hp cht ph hydrocacbon l cc hp cht
c hi cho qu trnh cracking xc tc.N khng ch u c xc tc m cng chuyn vo sn phm
v lm gim cht lng ca sn phm. Cn nguyn liu cng nng, cng cha nhiu asphan v kim
loi. Khi crcking cn phi qu x l bng hydro ho lm sch [3]
Nhit trong reactor
Nhit trong reactor l yu t tc ng trc tip n qu trnh to cc. Vic chn khong nhit
cho qu trnh l rt quan trng, va m bo v lng xng to ra va hn ch m mc thp
nht c th c ca qu trnh to cc [3]
p sut
p sut cng nh hng ln n qu trnh cracking, kh p sut tng ln s lm nguyn liu by
hi kh khn, lng hi nc qa nhit a vo thit b phn ng vi nguyn liu cn phi ln.
iu ny cng thy r khi ch bin cc nguyn liu nng khi tng p sut, cc sn phm nng ca
phn ng s chuyn sang trng thi lng. Trn b mt xc tc xy ra cc phn ng trng ngng bc
hai dn n tng vic to cc. V vy,qu trnh ny ch tin hnh p sut thng.[3]

30

Tc np liu ring ( hay tc khng gian np liu).

Tc np liu ring l t l gia lng nguyn liu c np trong mt n v thi gian trn
lng xc tc c trong vng phn ng. Tc np liu ph thuc vo nguyn liu v xc tc
dng trong qu trnh.
Khi tc np liu gim, su chuyn ho qa trnh tng ln, dn n hiu sut xng, kh ,
cc tng. Nh vy, khi gim tc np liu th thi gian lu li cc hydrocacbon ca nguyn liu
trong vng phn ng tng ngha l thi gian tip xc tham gia phn ng v xc tc tng. Khi tng
tc np liu nu ta tng nhit phn ng s tng tr s octan ca xng v tng hiu sut olefin
trong kh.Nh vy vic chn tc np liu thch hp s cho php hn ch lng cc to ra trong
qa

trnh,

em

li

hiu

sut

cao

[3]

30

PHN II: K THUT THC NGHIM.

II.1. nguyn liu v ho cht:
Nguyn liu: Cao lanh min Bc Vit Nam do b mn cng ngh vt liu Silict, Kho cng
ngh Ho hc trng i Hc Bch Khoa H Ni, cung cp
Ha cht: c s dng dng tinh th, nguyn cht v c pha ch cc nng d thch hp, do
cc nng thch hp, do cc nc Hugari, Lin x (c) Tip Khc (c), Trung Quc v vit Nam
sn xut. Bao gm: HCl, H2SO4 HNO3, CH3COOH, NaOH, NH40H, NH4Cl, TEA , BaCl2, NaCl,
La(NO3Cl), AgNO3.
Cc ch th Metydacam, phenolptalein.
II.2. Tng hp cht xc tc .
II.2.1 iu ch Zeolt X,P (dng NaXv NaP).
Zeolt X v Zeolt P c tng hp theo qui trnh thc nghim ca phng ho hc hu c.
Nguyn liu dng tng hp Zeolt X v Zeolt P
-

Cao lanh hot ho.

- Natri hydroxit NaOH

- Cht to phc (Ho)
- Mui natri clorua NaCl.
-

nc ct H2O.

- Thu tinh lng Na2Si03

-

Qu trnh thc hin : chia thnh 4 mu khc nhau c nh s mu A 1, A2,

A3 ,A4, nguyn liu c pha trn theo t l nht nh. Vi thnh phn s liu ban u cho qu trnh
tng hp c tnh theo t l mol nh sau:
K hiu mu

SiO2/A
l203 2,14
10
4

A1
A2
A3

Na2/
Si020,6
0,6
0,6

H0/
Me01
1
1

NaCl/A
l2O31
1
1

iu kin tng
hp24hgh,24hkt
48hgh,48kt
48hgh,48kt

A4
10
0,6
1
1
96hgh,48kt
Cc phn ng c gi ho v thc hin trong iu kin thu nhit nhit 90 0C c khuy.
Sau phn ng, cht rn c lc ra bng nc ct nhiu ln n khi nc ra ln cui ht cc mui
tan ri c a sy 1050C trong 3 gi, tip c nghin mn v ry ly c ht li 0,15 mm.
Cc mu c ly mt lng nh xc nh bng cc phng php hp th hng ngoi, nhit x
phn tch nhit, chp knh hin vi qut
II

2.2.

iu

ch

Zeolt

X v LaX LaY, LaP c iu ch bng cch trao i

dng

X,Y,

ion vi dung dch La(NO 3)3.0,5N

Qu trnh iu ch c th hin theo s :

30

Cch tin hnh : Cc Zeolt (X,Y,P) c iu ch dng NaZeolt trc tin cn tin hnh trao
i vi ion Na+ t dung dch La(NO3)3 nng 0,5N theo t l rn /lng: 1/10, a hn hp v dng
PH

=9

bng

cch

thm

dung

dch

NaOH.

Hn hp c khuy trn nhit phng, trong thi gian 8 gi. Sau lc v ra loi ion
NO-3 ra khi xc tc v ra sch bng nc ct qua nhiu ln, xc tc sau khi ra c sy s b
1050-C trong thi gian 2h ri em nghin ry ht di 0,25mm. Qu trnh c thc hin 3 ln.
Sau c nung nhit 300 0C trong 3h ,5000c trong 2h v 6000c trong 2h chuyn ht Na
zeolt v dng LaZeolt .
Phng php ny c u im l lm tng tnh axt ca xc tc rn nhng vn gi nguyn c
dng cu trc khi x l nhit ng thi lm cho xc tc c n nh cao.
II.3

Cc

phng

php

thc

nghim

nghin

cu

cu

trc.

Trong lnh vc khoa hc thc nghim c rt nhiu phng php khc nhau c s dng nghin
cu c tnh v cu trc tinh th ca vt liu. Vic la chn cc phng php ny ph thuc vo
tng loi cu trc v mc ch nghin cu. p ng yu cu t ra trong khun kh n ny
chng ti s dng nhng phng php nghin cu cu trc v nhn dng cc sn phm Zeolt
c iu ch sau:
-

phng php xc nh tng dung lng trao i cation (CEC) .

Phng php hp ph.

Phng php ph hp ph hng ngoi (IR).

hng php nhim x rnghen (XRD).

Phng php knh hin vi in t qut.(SEM)

Phng php phn tch nhit vi sai DTA.

Phng

php

th

hot

tnh

xc

tc

trn

phn

ng

cracking

n-

hexan.

II3.1. Xc nh tng dung lng trao i cation(CEC) [4]

Dung lng trao i cation ca vt liu mao qun phn no nh gi c kh nng hp ph,
in

tch

trong

khung

cu

trc

(lin

quan

Si/Al).

Dung lng trao i cation c tnh bng miling lng gam ca cation trao i trong 100gam
nguyn liu (mldl/100g)
Qu trnh trao i c thc hin nhit thng, cation trao i l Ba 2+, qu trnh c m
t
Me
Vi

bng
Zeo

phn

tng

Ba2+

+n
n

ng

in

tch

qut

sau:

nB-zeo

+2Mmn+

cation

Me.

Cc tin hnh nh sau:Cn 0,5 gam sn phm cho vo bnh tam gic 250ml, b sung thm 25 ml
dung

dch

BaCl2

0,05N.

iu chnh pH= 9(s dng dung dch NaOH nu PH<9 hoc dung dch CH 3COOH long nu

30

PH>9). Tin hnh lc trong vng 2 gi trn my lc c kh, tin hnh lc ra sn phm bng dung
dch BaCl2 v nc ct (ra sch ht Cl - )bng cch th dung dch AgNO 3 1% . Tin hnh sy kh
trn giy lc, sau chuyn vo bnh tam gic, b sung thm chnh xc 60ml dung dch H 2SO4
0,05N, lc lin tc trong 30 pht trn my lc em lc qua giy lc, thu c phn dch lc. ong
chnh xc 25ml dung dch lc, thm 23 git ch th phenophtalein, tin hnh chun bng dung
dch NaOH 0,05N cho ti kh xut hin mu hng nht, c v ghi th tch NaOH 0,05N chun
ht.
Qu trnh xc nh c tin hnh nhiu ln, mi ln c sai s khng qu 2% ly qu dng lng
c

tnh

nh
D

Trong

sau:

V1 V 2 .N .100.100
(mldl / 100 g )
V .C

v1- th tch dung dch NaOH 0,05Nchun vi mu (ml)(mu trng dung dch H 2SO4)
V2- Th tch dung dch NaOH 0,05N chun vi 25ml dung dch lc, ml;
N;

Nng

thc

ca

dung

dch

NaOH.

C: Trng Lng ca mu dng phn tch.

V Th tch nc li em phn tch .
100l 100ml H2SO4 cho tc dng vi cao lanh trao i Ba2+
100 Quy v 100 gam sn phm.
II.3.2 phng php hp ph:[7].
Qu trnh xc nh kh nng hp ph H2O v C6H6 c tin hnh nh sau:
Ly chnh xc 2g mu vo cc l phn tch nh (cc l bit trc khi lng). Cho c l
v mu vo trong thit b sy chn khng ( to=110oC)v sy trong 7h. Sau 7h, ly l cha mu
sy kh em cn xc nh trng lng mu sau khi tch nc hp ph. Sau khi cn, cho cc l
cha mu vo cc bnh kn c cha nc v benzen v iu kin tnh trong 14h. Sau khi hp
ph nc v benzen 14h, ly cc l em cn xc nh lng nc, benzen b hp ph. Cc qu
trnh cn, cho cc l vo hay ly cc l ra khi thit b sy, bnh hp ph phi c thao tc nhanh,
hn ch sai s mc ti thiu do thao tc v cc iu kin khch quan.
Dung lng hp th cng l mt trong nhng c trng quan trong ca loi vt liu mao qun c
b mt trong pht trin. Tuy khng phn bit gia cc kiu cu trc, nhng n cho thm nhng bng
chng v s ph hp vi vt liu cn so snh. N cng rt nhy vi s xut hin cc pha l, ngoi ra
phng php ny cn xc nh xp ca tinh th ph thuc vo tng dung lng trao i.
II.3.3 Phng php ph hp ph hng ngoi (I.R)[10]

30

Phng php ny da trn nguyn tc: khi chiu mt chm ta n sc c bc sng nm

trong vng hng ngoi (5010.000cm-1)
Qua cht phn tch mt phn nng lng b cht hp th lm gim cng tia ti. S hp th
ny tun theo nh lut Lambert- Beer {31}
D lg

I0
k .d .c
I

Trong
I0.I;

:D

cng

nh

;
sng

trc

mt
v

sau

khi

ra

khi

quang.
cht

phn

ng.

C; Nng cht phn tch.

Phn t hp th nng lng s thc hin dao ng (x dch cc ht nhn nguyn t xung quanh
v tr cn bng) lm gim di lin kt gia cc nguyn t v cc gc ho tr tng gim tun hon,
ch c nhng dao ng lm bin i momen lng cc in ca lin kt mi xut hin tn hiu hng
ngoi. ng biu din s ph thuc ca truyn quang vo bc sng l ph hp th hng
ngoi. Mt nhm chc hoc lin kt c mt tn s (bc sng) c trng bng cc Pic trn ph
hng ngoi. Nh vy, cn c vo cc nguyn t hay nhm nguyn t, t xc nh cu trc ca
cht phn tch.
II3.4. Phng php nhim x rnghen(XRD)[11]
Phng php nhim x Rnghen l mt trong nhng phng php c s dng kh ph bin,
nghin cu vt liu, c bit l trong nghin cu cu trc tinh th vt cht. Theo l thuyt cu to
tinh th, mng li tinh th c cu to t nhng nguyn t t ion phn cch gia nguyn t (hay
ion) khong vi amstron (A0) khi chm tia ti p vo mt tinh th v i vo bn trong n, th mng
tinh th c th ng vai tr ca mt cch t nhim x c bit. Trong mng tinh th, cc nguyn t
hay ion c th phn b trn mt phng (mt phng tinh th ) song song vi nhau. Cc nguyn t b
kch hot bi chm tia X ny s tr thnh nhng tm pht ra tia tn x. Hiu quang trnh ca hai tia
phn x bt k trn hai mt phng cnh nhau c tnh nh sau [31]:
=2.d. sin
Trong

d; khong cch gia hai mt phng song song

gc

gia

chm

tia

Theo iu kin giao thoa cc sng phn x trn hai

mt

phng

phn

x.

mt phng cng pha th hiu qu quang

trnh bng nguyn ln di sng ( ). Do .

2.d.

sin

=n.

y l h thc Vulf Bragg, l phng trnh c bn trong nghin cu cu to mng tinh th. Cc c

30

vo cc cc i nhiu x trn gin nhim x Rnghen xc nh c 2 . T tnh ra d theo h

thc Vulf- Bragg; so snh ga tr d tm c vi d chun th s xc nh c thnh phn cu trc
mng tinh th cu cht phn tch. V vy , phng php ny thng c s dng nghin cu
cu trc tnh th v vt cht.
II.3.5

Knh

hin

vi

in

qut

(SEM)[11]

nguyn tc c bn ca knh hin vi in t qut l dng chm in t to nh cho mu nguyn

c,

nh

khi

mn

hunh

quang

th

phng

yu

cu.

Chm in t c to ra t catt (sng in t) qua hai t quang s c hi t ln mu nghin

cu . Chm in t c qut ln mu, s pht ra nhng in t phn x th cp. Mi in t phn
x ny qua in th gia tc vo phn thu v c bin i s tr thnh mt tn hiu nh sng, chng
c khuch i v a vo mng li iu khin to sng trn mn nh.
sng ti trn mn nh tu thuc vo lng in t th cp pht ra ti b thu v ph thuc tnh
trng b mt mu nghin cu. c bit do c kh nng hi t chm tia nn chm in t c th i
su

vo

trong

mu,

cho

php

nghin

cu

phn

bn

trong

ca

vt

cht.

Nh kh nng phng i v to nh mu r nt, hin vi in t qut thng c s dng nghin

cu

kch

thc

hnh

dng

tinh

th

vt

cht.

II.3.6 Phng php phn tch nhit vi sai.[12]

C s l thuyt : nguyn l chung ca php phn tch nhit c th da trn hai phng php sau:
-

Nguyn

-Chun

ho

do

Vi

sai:

trong

phn

tch

nhit.

Phn tch nhit theo trng lng ( TGA) mc ch l kho st s thay i trng lng theo nhit .
Phn tch nhit vi sai (DTA) l kho st s thay i theo nhit khi thc hin chng trnh nhit
. T hai kt qu ny c th d on s thay i vt liu khi tng nhit . Qua cc mu phn tch
chng

ti

thc

hin

phng

php

phn

tch

nhit

vi

sai

(DTA).

II.3.7. Phng php nghin cu hot tnh xc tc [3].

Phng php nghin cu hot tnh xc tc l mt trong nhng phng php ph bin xc
nh cc c trng nh tnh axit, tnh cht chn lc ca Zeolt , t php hin c kh nng v
phm

vi

ng

dng

ca

xc

tc

ti

ca

cc

mu

nghin

cu.

Mt khc s tng quan gia tnh cht axt ca xc tc rn v hot tnh xc tc ca chng trong
phn ng hydrocacbon l kh phc tp. Do , hot tnh xc tc l mt c trng quan trng ca
tng loi xc tc. Ngi ta s dng cc phn ng mu nh cracking (n-Hexan), ng phn ho nButen, alkyl ho benzen c trng cht xc tc. Qua y chng ti dng phn ng cracking
n-Hexan

xc

nh

hot

tnh

cc

xc

tc

zeolt

(X,Y,P).

Trong phn ng cracking n-Hexan ,hot tnh cc xc tc zeolt c xc nh trong h vi dng. Tc

np liu l 18,5ml/h , khi lng xc tc l 5gam, thi gian phn ng l 64 pht 52 giy nhit

30

phn

ng

thay

2200C

4000C

Cht xc tc c kho st hot tnh trng thi ban u l trng thi b mt xc tc cn mi

nguyn, hoc trng thi n nh l trng thi xc tc sau nhiu chu trnh phn ng v hon nguyn
n khi hot tnh v hiu sut to cc sn phm hu nh khng thay i. Hon nguyn xc tc sau
mi ln phn ng bng dng khng kh m i qua xc tc nhit cao hn nhit phn ng
trong 2 gi. Hon nguyn xc tc zeolt khi c mt hi m s c tc dng lm gim qu trnh
dehydroxyl ho bmt xc tc v th tc ng c li n hot tnh xc tc .
1. s thit b phn ng v nguyn l lm vic.
Vic

nghin

cu

hot

tnh

cc

xc

tc

theo

hai

hng

chnh.

* Thc hin phn ng cc xc tc thay i theo nhit khc nhau t (220 0C 3000C,3500C,4000C)
Mc ch phng php ny l tm ra nhit ti u cho tng loi xc tc hay tm ra hot tnh cao
nht ca tng loi xc tc theo mt nhit nht nh.
*Nghin cu cc xc tc thay i theo thi gian ti nhit ti u, nhm mc ch cng xc
nh hot tnh cc xc tc v tm ra n nh v thi gian lm vic ca tng loi xc tc.
Trc khi thc hin cc xc tc c p thnh vin sy kh, to ht c kch thc > 0,25
nhng < 0,6. Trc khi phn ng xc tc c hot ho 2 gi nhit 400 0 C trong khng kh
kh.
a. S thit b phn ng
b. Nguyn l lm vic ca s
*Cc thng s c trng cho xc tc .
chuyn ha chung ca n-Hexan nghin cu c xc nh theo cng thc sau :

m 0 m1
x100%
m0

Trong

m0 : l lng nguyn liu (n-Hexan) trc phn ng, mol.

m1
2:
*

lng

sn

hot

tnh

phm(

chuyn
xc

tc

Hexan)

ho
c

xc

sau

phn

chung,
nh

theo

ng,
%

cng

mol.
mol

thc

sau:

m 0 m1
(mol / gxth)
m xt
Trong : m0 : lng nguyn liu (n-Hexan) trc phn ng

30

m1:

lng

sn

phn

(n-hexan

sau

phn

ng,

mol.

mxt lng xc tc a vo s dng .

chn

lc

sn

phm

tnh

theo

cng

thc

sau:

0
x100%
1

Trong : 0 :l chuyn ho thnh sn phm chnh, %mol.

x1 : chuyn ho chung, %mol.

30

Phn III
Kt qu v tho lun.
III.1. Cc phng php c trng cu trc.
III.1.1. phng php trao i cation..
Xc nh tng dung lng trao i cation (TDLT) CEC nhm mc ch nh gi kh nng ph
v cu trc cao lanh ca cht to phc cng nh chuyn ho cu trc cao lanh thnh cu trc Zeolt
chng ti tin hnh xc nh theo cc mu iu ch A1, ,A2 ,A3 ,A4 ,A5 kt qu c xc nh
bng 12 thy rng cc mu iu ch A1, ,A2 ,A3 ,A4 ro vi mu chun A5 ta thy tng dunglng
cc mu iu ch rt cao. c bit l mu A4 gn tng ng mu A5. iu ny c th gii thch
rng nn nh dung lng trao i cation m cao th chng t cu trc cao lanh ban u dn bin
iqua cc pha khc.Tc l s thay i rt ln v cu trc cao lanh ban u. S tng TDLTDC cc
mu l A1 n A4 chng t cao lanh bin i cn trc sang pha Zeolt.

php

nh ga tng i v cu trc ca cc zeolt sau khi iu ch ti thc hin phng

hp

ph

nc

Benzen.

III.1.2 Phng php hp ph nc v benzen.

Cc mu sau khi iu ch, cho hp th vi H2O v ben zen. Kt qu thc nghim bng 12 cho
thy mc hp th cc mu trong nc v Benzen rt cao gn bng mu chun A5 . c bit l
mu A4 hp ph tng ng vi mu chun A5. iu ny cng cho thy c cu mu iu
kin ch cng c hp ph cao gn nh mu chun. Chng t cc xc tc sau khi iu ch c
xp rt tt. Kch thc mao qun ln thun li cho qu trnh chn lc SP.
III.1.3 Phng php hp th ngoi (IR) .
Kt qu phn tch hng ngoi ca cc mu A1, A2 A3 A4, tng hp c ch ra hnh ( ) ph c
chp trong dao ng tinh th c trng cu trc zeolt. Cc m ph t 400 cm -1n 800 cm-1 v t
800cm-1 n 1000cm-1 .c trng cho cc dao ng t din TO 4(T=Si v Al) chng c mt hu ht
cc aluminosicat tinh th v v nh hnh. Cc m ph t 600cm -1 n 1000cm-1 rt ch trng cho
tinh th zeolt X so vi mu chun.
Nhn thy rng, cc m ph c trng ca zeolt Xv P u xut hin c sc nt. Nh vy,
c th kt lun zeolt X,P c hnh thnh c hiu sut cao.
nghin cu chi tit hn v cc mu nghin cu, chng ti chp ph nhim x Rnghen
III.1.4.Ph nhim x Rnghen(XRD).
T ph nhim x Rnghen cc mu phn tch c th thp cc cc i nhim x trong vng 2
t 0 dn 10 c trng cho Zeolt u xut hin cng mnh. T 10 n 35 c trng cho Zeolt P
xut hin cc Pic c cng cao. Cc m ph ca mu tng hp u trng vi mu chun trong

30

Atlas

(cc vch thng ng lng trong vch ph) hnh theo s cc mu.

Ngoi ra cc phng php nhim x Rnghen ( XNO) cn cho ta xc nh c hiu sut v tng
loi zeolt c th theo bng sau.
Bng

Thnh phn %
III.1.5.

phng

php

phn

tch

nhit

vi

sai

(DTA).

xc nh r v s bin i cn trc cc loi zeolt nhit chng ti thc hiu php nhn tch
nhit vi sai cc mu iu ch. iu kin phn tch nhit 700 0C trong thi gian 10 pht vi
kh phn tch khng kh qua kt qu phn tch nhn thy cc pc cu mu iu ch gn ging nh
mu chun chng t c s thay i nhit theo cu trc. S phn tch nhit vi sai Hnh (.0
III.1.6.

phng

php

knh

hin

vi

in

qut

(SEM)

Ngoi cc phng php trn chng ti cn phn tch cu trc ca Zeolt bng knh hin vi in t
(SEM) nhm mc ch xc nh c b mt, kch thc, hnh dng vi tinh th. Qua cc mu
phn tch cho thy c b mt, kch thc, hnh dng cc mu A1 A2 A3 A4 c dng gn ging nh
mu chun A5. iu ny chng t rng mu iu ch cao lanh Vit Nam cng tt ngang mu iu
ch

Si

Al

ring

l.

III.2.Nghin cu hot tnh cc xc tc LaX, LaP, LaY

III.2.1 Xc nh hot tnh cc xc tc zeolt LaX, LaP, LaY theo nhit trn phn ng
Cracking( n Hexan).
Xc tc sau khi tng hp dng LaX, LaP, LaY dng ny hu nh cha c hot tnh. xc
nh hot tnh xc tc trc tin ta phi chuyn v dng zeolt (NaX, NaP, NaY) sang dng
Zeolt(LaX, LaY LaP) bng cch trao i ion vi dung dch La(NO3)3 0,5N theo t l 1 gam mu
10ml dung dch.
Cc xc tc c th hot tnh trn s phn ng vi dng ti phng th nghim hu c ho
du.
Kt qu thc nghim hot tnh xc tc v chuyn ho cc zeolt (LaX, LaY, LaP) ti cc
nhit c th hin bng 1 v th 1
T kt qu thc nghim v trn th ta xc nh c chuyn ho v hot tnh cc xc tc
zeolt (LaX, LaY, LaP) ti cc nhit ti u cho tng loi xc tc sau khi lm vic . c bit xc
tc LaX c chuyn ho v hot tnh cao nht ti nhit 3500C t30% cn Zeolt LaY c hot
tnh cao ti 3000C t 35% cn Zeolt LaP cc i trn nhit 400 0C).iu ny c th ni rng
hot tnh xc tc ca zeolt iu ch t cao lanh cng cao gn tng ng vi zeolt chun i t Si
v nl ring l.
Mt khc, trn cc xc tc khc nhau qu trnh cracking ph thuc vo nhit l khc
nhau, zeoltLaX1 c chuyn ho cng nh hot tnh thp hn so vi zeolt (LaX, LaY, LaP) ti

30

3000C. Chng t rng ti nhit ny xc tc Zeolt LaY cho chn lc, kh nng khuch tn v
ph thuc trn tm hot tnh xy ra phn ng cracking l ln sau mt hot tnh v gim dn.
c bit ti nhit 4000C th LaP li cho chuyn ho v hot tnh xc tc cao nht
chng t hp ph trn cc tm hot tnh ca zeolt LaP ti nhit ny khng km so vi LaY
chun.
Mt iu ng ch l trng thi ban u ca cc loi xc tc nhit thp cho chuyn
ho v hot tnh hu nh thp hn hn khi tng nhit cho qu trnh. Nh vy qu trnh cracking
cn chn mt nhit thch hp v hp vi tng loi xc tc th khi chn lc sn phm cng
nh hiu xut chuyn ho l cao nht .
tm c thi gian lm vic v mc n nh ca tng loi xc tc, chng ti nghin cu
chuyn ho v hot tnh cc xc tc Zeolt(LaX, LaY, LaP) theo thi gian trn phn ng
Cracking n- Hexan
III.2.2 Nghin cu s thay i chuyn ho v xc tc theo thi gian (pht)
Vic nghin cu ny cng trn s phn ng vi dng ti phng th nghim hu c ho du
.Kt qu v th bng v hnh Qua kt qu chng ti xc nh c thi gian lm vic c th
ca tng loi zeolt. Da vo th xc nh c thi gian lm vic
Ca cc xc tc n nh khong 10-15 pht c bit l xc tc Zeolt LaX c chuyn ho v
hot tnh v thi gian lm vic gn tng ng vi xc tc Zeolt LaY chun , cn zeolt LaP tuy
c chuyn ho v hot tnh thp hn nhng thi gian lm vic hu nh tng i di v n nh
nht so vi Zeolt LaX v Zeolt LaY chun. Nh vy, cng chng t c rng xc tc zeolt LaX
v LaP c iu ch t cao lanh Vit Nam cng c hot tnh cao v thi gian lm vic n nh rt
tt khng km g xc tc c iu ch t ngun Si v Al ring l.
Mt khc, theo s liu v th cng cho thy c chuyn ho v hot tnh xc tc cc
xc tc zeolt lc u gi mc n nh sau gim dn .Mc n nh xc tc hu nh bng
nhau . Mt d chuyn ho v hot tnh c khc nhau, nhng vi mc n nh nh vy cng c
th gii thch c rng mc lin kt Si- 0H-Al v Si-0H- Si trong cc xc tc hu nh tng
ng nhau . Nh vy khng nh rng cc xc tc iu ch c hot tnh v n nh tt .
III.2.3 Nghin cu s thay i sn phm .
Sn phm l mt trong nhng yu t quan trng trong qu trnh crckinh xc tc. c dc sn
phm mong mun th cn phi chn ch cng ngh , xc tc ,nhit thch hp nhm mc ch
em li

sn phm mong mun v c chn lc ca nht .

Kt qu nghin cu hot tnh cc xc tc Zeolt (LaX,LaY,LaP),cng cho thy rng cc xc tc

ny c chuyn ha v hot tnh cao ,cng vi vic chn lc trong qa trnh phn tch v so snh
thnh phn phn tch mu chun chng ti a ra thnh phn sn phm c trng ca qu trnh
crckinh (n-Hexan) cc nhit ti u ca qa trnh cho cc loi xc tc nh sau:

30

T cc s liu bn cho thy thnh phn phn trm theo sn phm c trng trong qa trnh
crackinh (n-Hexan) tng i cao cc sn phm nh propan,propen.c bit hai xc tc Zeolt
LaX v Zeolt LaY s phn b sn phm gn nh nhau.Nh vy c th gii thch l do lc axt v tr
tm t din T04, cng nh hot tnh Zeolt LaY v Zeolt LaX gn nh nhau, trong Zeolt LaX
c phn nh hn Zeolt LaY nh khng ng k . Nh vy, chng t xc tc iu ch t cao lanh
Vit Nam tng ng xc tc iu ch t ngun Si v Al ring l. iu ny thun li cho vic iu
ch

Zeolt

Cao

lanh

Vit

Nam.

TI LIU THAM KHO

I. ti liu tham kho ting vit.
1.

inh Th Ng ha hc du m .Trng i Hc Bch Khoa H Ni 1999.

2.

Nguyn Phi Hng Crckinh huydrocacbon trn cc xc tc cha Zeolt ZSM-5. Lun

n tin s ho hc. H Ni 2001

3.

L Vn Hiu cng ngh ch bin du m i Hc Bch Khoa H Ni 1978.

4.

T Ngc n Lun n tt nghip cao hc 1999.

5.

Phm L H Lun n tt nghip cao hc 1999

6.

Bi Vn Hi Lun vn thc s ha hc 1995.

7.

Nguyn Hu Ph . Hp ph v xc tc trn b mt v c mao qun nh xut bn

KHKT .H Ni 1998.
8.

Trn Trung Ninh .Zeolt ZSM-5 tng hp c trng v tnh cht

xc tc .Lun n

tin s ha hc ,H Ni 1999-2000.
9.

Phm Phc Ho Lun n tt nghip cao hc 1999-2000.

10.

Nguyn Hng Lin Lun n tt nghip cao hc 1998.

11.

T Vn Mc phn tch ha l ,NXB KHKT 1995.

12.

V Vin Ry Phn T tng hp c trng v tnh cht xc tc.Lun n tin s ho hc

,H Ni 2000.

II. Ti liu tham kho ting Anh.

13.

Baron Cronstedt , Akadp . Hanh .Stockholm 18,120,1756.

14.

JW. Macbain the Sorption of Gases , Rutlege,1932.

30

15.

A.Dyer ,An Introduction to Zeolte molecular ,steves., JWley Sons Ltd,1988.

16. Scherzer

Julius . Dctane Enhancing , Zeolte FCC catalysisscientific and technical

aspets .Catal .Rew.Sei .Eng,P.215-354 (1989).

17. Frilette V.J .and P.B Weisz ,US . patent ,No.3508867(1970).
18. P.W .Breck . Zeolte Molecular Seive .Advan .Chem

ser .,101,american ,chemistry

Society ,Washington D,C ,P11 (1974).

J,V.Smith . Minaral. Soc .Amer . Spec ,Pap . N01 (1963).

19.
20.

Breck D . W .(1969),U . S Patent 3130007.

21.

C . Naccache , Ecole catalyse VietNam 1996.

22.

Donald W. Breck Zeolte molecular sievers.

23.

Le Cong Hoa Rapport de stage scientifigue , Grenoble ,1991.

24.

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sijhoff and Noordhoff , Alphen aan den Rijn ,the Netherlands ,P .137.
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protolytic of alkanes ,Microporous and mesoporous materials, 35-36, pp.11 20.

26.

De kroes B., Groenenboom C.J., O Connor P. (1986). New Zeolite in FCC, Ketjen

catalysts Symposium, the Netherlands, F1.

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M. Guisnet, G. Perot. Zeolite bi Sunectional catalyss Zeolite. Science and

technology( 1984)
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Eastwood S.c, DrewR.D, hartZellF.D(1962) al & Gas J., 60, p 152.

Gates B.C, Katzetr,J.R .schuit.G.C.A(1979) chemistry at catalits processer MC graw

Hill, NEW YOUK.

30.

bruces Gates, jamesr. Katzer, schuit.G.C.A(1979) chemistry at catalits

processer .MC Graw Hill book company.

31. Greensfelder B.S, Voge H.H ,good G.M (1949), Ind. Eng,chem;41 p-2573.
32.

D.W. Breck Zeolites molecular seive. Advan. Chem, sev.,101,american, chemistry

socicty. Washington D.C ,P 11(1974).

33.

P. Gallezot. Let zeolite, recrwerl des confererences, lycon(1974).

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