I/ Gii thiu v Zeolite

1/ Ngun gc- nh ngha:

Theo ting Hy Lp Zeo: si, Lithot: , v vy zeolite
c ngha l si.
Zeolite bt u c pht hin t nm 1756 bi Cronsted.
Bronstedt l mt nh khong hc ngi Thy in pht
hin ra mt loi khong mi vi tn gi Zeolite. ng pht
hin ra Zeolite nh hi nc thot ra khi nung khong ny.
Nm 1944, Barrer v Ibbitson ch ra hiu ng ry phn
t cho php tch cc n v iso-parafin.
Nm 1956, cc Zeolite u tin c tng hp.
Hin nay c khong hn 15000 cng trnh cng b v
10.000 pht minh sng kin tng hp zeolite.
Nh vy zeolite c tm quan trng ln lao trong khoa hc
v k thut.

Zeolite qua knh hin vi in t-

trong t nhin

2/ Phn loi
Phn loi

Theo
kch thc
mao qun

Theo
thnh phn
ha hc

Phn loi da theo kch thc

mao qun
mao qun rng
7 8 A0

mao qun trung

bnh
5 6,9 A0

S nguyn t O
trong 1 ca s

mao qun hp

ng knh
mao qun ( A0 )

< 5 A0

Loi zeolite

8 ( mao qun hp )

4,3

A , Erionit

10 ( mao qun trung

bnh )

6,3

ZSM-5,
Ferrierit

12 ( mao qun rng )

8,0

X, Y, Mordenit

Phn loi theo thnh phn ha

Theo quy tc Loweinstein xc
nh rng :
hc
2 nguyn t Al khng th tn ti ln cn nhau, ngha l cu trc zeolite

khng th tn ti cc lin kt Al-O-Al m ch c cc lin kt Si-O-Al hay Si-OSi

Ni cch khc ch tn ti loi t l Si/Al 1

H zeolite
anuminophotphat

Zeolite giu Si
tch Al
Ry phn t zeolite

Zeolite ngho Si giu Al

TPHH

Zeolite c hm lng
trung bnh
Zeolite giu Si

Phn loi theo thnh phn ha

hc
Zeolite ngho Si giu Al

Phn loi theo thnh phn ha

hc

Zeolite c hm lng Si trung bnh

Phn loi theo thnh phn ha

hc
Zeolite giu Si & ry phn
t
zeolite
Zeolite giu Si

Ry phn t zeolite

Phn loi theo thnh phn ha

hc
Zeolite giu Si tch nhm
Bng cc phng php sau tng hp , ngi ta c th bin

i thnh phn ha hc ca zeolite. Mt s phn ng ha hc

c th tch Al khi mng li tinh th v thay vo l Si
hoc nguyn t ha tr III hoc IV khc. Phng php ny c
gi l phng php loi nhm tc l dsalumination.

Thng thng ngi ta dng zeolite X hoc Y c t l Si/Al =

1,2 2,5 , sau khi loi nhm th thu c zeolite giu Si c t

l Si/Al 9. vi phng php ny nu zeolite thu c c t l
Si/Al > 9 th s ph v mng li tinh th ca zeolite.

Phn loi theo thnh phn ha

H zeolite aluminophotphat
hc

( AlPO )

Gn y c mt h cht rn mi c cu trc tinh th tng t zeolit gi

l Aluminophotphat (AlPO) c pht minh bi cc nh nghin cu

ca Lin hip Carbide trn c s cc nguyn t l Al v P.
Vt liu ny khng c cu to t cc t din SiO 4 v AlO4- m c
cu to t cc t din AlO4- v PO4+ theo t l 1:1 nn trung ha v in
tch.
V cu trc trong h ny c loi AlPO-5 c cu trc hnh hc tng t

h Faujazit v loi AlPO-11 c cu trc hnh hc tng t zeolit ZSM-5.

Cc c trng c bn ca cc AlPO l u c t l Al/P = 1, khng c
mt ca cacbon b tr, khng c kh nng trao i cation v v vy
khng c tnh xc tc.

Phn loi theo thnh phn ha

hc
H zeolite aluminophotphat
( AlPO )
Cc bin tng ca AlPO l SAPO v MeAPO.
SAPO: khi a vo AlPO mt lng nh Si thay th P th vt liu

thu c gi l SAPO vi khung in tch m v do c kh nng

trao i cation.
MeAPO: nu a cc nguyn t khc nh Co, Mn, Fe, V, Ga... vo

SAPO th nhn c h ry phn t mi, k hiu l MeAPO, km

theo l s thay i tnh cht axit - baz, oxy ha kh ca vt liu.
V cu trc hnh hc cc vt liu Co-APO, Mn-APO, V-APO c cu
trc tng t AlPO5, AlPO11, AlPO17, AlPO31.

3. Cc loi Cu trc
Zeolit
a.
b.
c.
d.

Cu trc Zeolite tng qut

Cu trc Zeolit A, X, Y
Cu trc ZSM5
Cu trc USY

Ngoi ra cn c zeolite aluminophotphat

cu to t cc t din AlO4- v PO4+ nh
AlPO-5 (ging Zeolite X,Y) ALPO-11(ging
ZSM5).

3. Cc loi Cu trc
Zeolit
a. Cu trc Zeolite tng
qut:
Cng thc chung:

Me2/n.Al2O3.xSiO2.yH2O
Me: kim loi kim hay kim th
n:ho tr ca kim loi

3. Cc loi Cu trc
Zeolit
Cu trc s cp
1.Tm: Al hay Si
2.nh: O

3. Cc loi Cu trc
Zeolit
a. Cu trc Zeolite tng
qut:

Cc t din trn lin kt vi nhau qua

nguyn t oxy thnh Cu trc th cp

b. Cu trc Zeolit A, X,Y

Cu trc th cp: hnh bt din ct gm
:

8 mt lc
6mt vung
24 nh(Si v Al)
36 cnh (v tr ca O)

b. Cu trc Zeolit A, X,Y

Cu trc Zeolit A
(LTA)

Cc soalit ghp ni vi
nhau ti cc mt 4cnh
thng qua trung gian
lng tr to thnh
Zeolite A

b. Cu trc Zeolit A, X,Y

Cu trc Zeolit A (LTA)

LTA

LTA

b. Cu trc Zeolit A, X,Y

Cu trc Zeolit X,Y

Sodalit ghp vi nhau ti cc

mt 6cnh thnh Zeolite X,Y

kch thc l Zeolite A< X,Y
T l Si/Al ca Zeolit X<Y

b. Cu trc Zeolit A, X,Y

Cu trc Zeolite X

FAU

c. Cu trc USY

Zeolite siu bn
Xc tc mi yu cu
USY
tch bt Al ra khi mng
Zeolite, gim hm lng
Na trong Zeolite tng
kh nng to olefin.
Zeolite siu bn
(UltraStable Y : USY).
bn cao hn nhiu
so vi Zeolite Y truyn
thng.
27

d. Cu trc ZSM-5

Cu trc th cp:
12 t din SiO4/2 v
AlO4/2 ghp vi nhau
nh hnh bn to

d. Cu trc ZSM-5

Cc chui
lin kt
thnh lp

d. Cu trc ZSM-5

4. Tnh cht b mt ca
Zeolit

Tm axit

Tnh chn lc
hnh dng

Trao i ion

4. Tnh cht b mt ca
Zeolit
a. Tnh trao i ion

oxy ha ca Si:+4, Al:+3

Tm
Tm

Si trung ha in

Al tch in m trung ha
bi 1ion dng( ion kim hoc kim
th) trao i ion

a. Tnh trao i ion

a. Tnh trao i ion

o
o

Khng lm thay i cu
trc tinh th
v tr khc nhau, tc
trao i khc nhau
v tr m(b mt) : d
dng
v tr kn (soalit,
lng tr): kh khn

a. Tnh trao i ion

tng trao i ion:

o x l vi dd cha ion trao i nhiu ln
o Gia cc ln phi sy kh v x l
nhit(nung 5000C)
Phn b ng u cation cc v tr
khc nhau
1phn cation di chuyn t v tr kn
m
d trao i

4. Tnh cht b mt ca
Zeolit
b. S hnh thnh cc tm axit

Trao i ion hnh thnh tm axit

Qu trnh hnh thnh tm axit:

Tm bronsted

T 0C

Tm
Lewis

Cc ion nh
Na+,Mg2+ hay proton
s trung ho in
tch ny v hnh
thnh tm axit
Bronsted
Khi tin hnh x l nhit khong nhit
400 500oC th xut hin cc tm axt
Lewis theo s sau:

4. Tnh cht b mt ca
Zeolit
b. S hnh thnh cc tm axit
o Cc Tm axit to nn hot tnh xc tc
o T l Si/Al tng s tm axit gim,

bn tm axit tng

o v tr khc nhau linh ng ca

cc proton khc nhau axit khng

ng u.

4. Tnh cht b mt ca
Zeolit
c. Tnh chn lc hnh hc

4. ng dng ca Zeolit

Cc qu trnh tch

Lm cht xc tc

Trong ha phn tch

Lm cht trao i ion

4. ng dng ca Zeolit

Tch C2H2 ra khi butadien,

khng kh lng
Tch NO ra khi kh v cht lng

ng dng cho
cc qu trnh
tch

Lm kh cc cht lng v hi
Tch hi du khi kh nn
Tch CO khi He v H2

4. ng dng ca Zeolit

Ha
phn
tch

4. ng dng ca Zeolit

Nhng cation kim loi c th b

tch ra khi nc thi : Cu2+ , NH+4,

Pb2+ , Zn2+ , Hg2+ , Cr3+ , Fe3+ , Cd2+ ,
Ca2+ , Al3+ , Cs2+ , Sr2+ .

c trao i vi Ag to thnh
NaAAg, gii quyt 1 lng nh nc
ngt khi gp nn bin

4. ng dng ca Zeolit

Lm cht xc

tc cho phn
ng ng phn
ha C5, C6 nhm
nng cao ch s
octan

Lm cht xc
tc

Lm cht xc tc
cho qu trnh
Cracking,ehydro
, ehydrat ( USY
dng trong FCC )
Fe-ZSM-5 : xc
tc cho phn ng
phn huy N2O ,
oxi ha hp cht
thm

Dng lm cht
mang cho cc
loi xc tc khc.

Gas separation membrane using zeolite

Zeolite Gas-Pump With No Moving

Parts, But With A High Rate Of Gas

Flow

Dr Peter Maier-Laxhuber & Zeolite Cooler

Dr. Peter Maier-Laxhuber, et al.

Zeolite Heat

Pump with
Integrated IceStorage

Oil

Purification
Zeolite
Station MCU4,3

II/ TNG HP ZEOLITE

1. Nguyn tc chung

Zeolite l cc aluminosilicat ngm nc,

c hnh thnh di cc iu kin thu
nhit
Ngha l mt h lng, cha cc thnh
phn ho hc thch hp c kt tinh
di tc dng ca nhit.

Phn ng thu nhit l

g?

Co nhieu nh ngha va nhan nh khac nhau : Morey &

Niggli (1913) , Rabenau (1985) , Lobachev (1973) ,

Yoshimura(1994)
Phan ng thuy nhiet la bat c phan ng d the vi
s co mat cua dung moi (nc hoac khong phai la
nc) dien ra tai nhiet o ln hn nhiet o phong va
ap suat ln hn 1 atm trong 1 thiet b kn.
V phan ng dien ra can s co mat cua pha long nhng
nhiet o can at ti lai qua cao khien cho pha long
khong ton tai c nen phai dung en ap suat cao e
at en nhiet o cho phan ng xay ra ma van am
bao con moi trng cho cac tac chat
Qua trnh thuy nhiet c tien hanh trong cac thiet b
chu ap suat cao va nhiet o cao goi la autoclave

1. Nguyn tc chung
ieu kien tong hp
Zeolite
Nguyn liu u: hot tnh cao
pH mi trng: kh kim
Nhit : thp
p sut: thc hin p sut hi bo ha ca

nc
Mc qu bo ha ca dung dch kt tinh phi

ph hp khng qu ln cng khng qu b.

Qu trnh kt tinh Zeolite gm cc giai on:

Qu trnh to gel: quan trng nht

o

Ch xy ra trong dung dch, mi trng kim mnh

Ch to thnh trong khong gii hn t l Si/Al thch hp

Hnh thnh lin kt Si-O-Al trong khung gel do tng

tc ca dd silicat v aluminatephn ng a trng
ngng:

Qu trnh lm mui: cn thit cho to

mm tinh th
o Mm tinh th bt u hnh thnh trong pha

lng ca gel hoc ti b mt phn cch pha (

gel-dd)
o Khi cu trc tinh th c to t cc t din

[SiO4] v [AlO4]

Pha rn v nh hnh

Pha lng
Gel aluminosilicate ban u
un nng

Pha rn
v nh hnh

Kt tinh gel
t0C ha tan lm nng tng

T xc tc lm tng tc
ha tan pha rn v nh hnh

Pha lng
phn ng
a t

Hnh thnh
mm tinh th

Kt t li thnh
tinh th zeolite
SN PHM KT TINH

QU TRNH KT TINH ZEOLITE

Qu trnh lc ra:
o Loi lng kim cha trong cc xoang

tinh th. Cng sch kim, cht lng

Zeolite cng cao
o Thc t, pH nc ra cn khong 8-9 l
t yu cu.

Cc yu t
nh
hng
n qu
trnh tng
hp
Zeolite

Trong cc yu t nh hng qu trnh kt tinh, bn

cht v tnh cht zeolite, thnh phn gel ban u l
quan trng nht.

Na2SiO3

NaOH

Al(OH)3

H2O
NaAlO2

H2O m
Lm mui

H2O

Lc
H2O thi

To gel

Kt tinh

Sn phm

S QUY TRNH TNG HP ZEOLITE

2.Tng hp Zeolite t hp cht v c

khng c cu trc
a. Phng php tng hp
zeolite A

Nguyn liu
Cc Zeolite t nhin c tinh ch, loi b tp

cht.
Cc ngun nguyn liu t nhin: kaolin, t st
c bin tnh bng ha cht
Thnh phn gel:
SiO2/Al2O3 = 1,3- 2,2
Na2O/SiO2 = 1,7- 2,8
[Na2O] =0.33- 0.92 mol/l

a. Phng php tng hp

zeolite A

Phng php 1:
To gel aluminosilicat t thy tinh lng hay tinh th
natri silicat trn vi natri aluminat bng cch khuy
trn nhit phng ( thng l 3 gi)
Kt tinh hn hp trn iu kin bnh thng (theo
nh s kt tinh nu phn trc).
Phng php 2:
To gel ban u bng cch rt dung dch natri silicat
vo natri aluminat trong kim nhit kt tinh v
khuy u.
Tinh th Zeolite thu c trng hp ny c kch
thc ln hn cch tng hp theo phng php 1.

a. Phng php tng hp

zeolite A
Phng php 1:

Phng php 2:

t0 phng

t0 kt tinh
khuy u

Na2SiO3

NaOH

Al(OH)3

Na2SiO3

H2O
NaAlO2
To gel

NaAlO2

NaOH

To gel

a. Phng php tng hp

zeolite A
Cc yu t nh hng
Nhit : tng hp p sut thng th khong nhit
dao ng kh rng.
p sut: thng tng hp p sut kh quyn.
Thi gian kt tinh: t 8-12h trong u kin khuy lin tc
nhit ~90oC.Nu nhit tng th thi gian kt tinh sn
phm gim i.
Hm lng kim: nng qu cao th thi gian kt tinh di,
nhng nng thp th kh kt tinh c gel aluminosilicat.
Hm lng nc: nh hng n qu trnh to gel ban u,
hm lng nc cng cao th trng kt tinh ca NaA cng
rng

a. Phng php tng hp

zeolite A

b. Phng php tng hp zeolite

X,Y
Zeolit X: SiO2/Al2O3 =2-3 ;

Zeolit Y: SiO2/Al2O3 = 4

Nguyn liu: natri silicat, natri aluminat, NaOH v cc

cht khc.
Thnh phn gel tng hp Zeolite NaX:
SiO2/Al2O3 = 2,2-3.2
Na2O/SiO2 = 1.0-2.3
H2O/Na2O =25-65
Thnh phn gel tng hp Zeolite Y:
SiO2/Al2O3 = 8
Na2O/SiO2 = 0.4
H O/Na O =10

Dd c khuy
trn, kt t
thnh ta gel xp
Aluminosilicat

NaAlO2
Na2O.nH2O
TB phn ng
TB kt tinh

Tch dd thu kt ta
hydro Aluminosilicat Lc khung bn
Loi kim d

Kt tinh
Zeolite A: 80-90oC trong 6h

Zeolite X: 95-100oC trong 12h

Zeolite Y: 990C trong

10h. pH 10,5

Ra
Nghin

m 35%

To vin

120-150oC

Sy

Loi bi

Sng quay
L nung
zeolite

30-40 ph
m 35%

Tng hp
zeolite loi
X,Y
575-6500C
624h
Dng tinh th

c. Phng php tng hp

USY
Cc phng php iu ch zeolite Y c t
s Si/Al cao
Tng hp zeolite Y c t s Si/Al ~2.5, sau tng t s Si/Al

bng phng php sau:

X l nhit v nhit hi nc
X l ha hc
Kt hp x l thy nhit v x l ha hc

Tng hp trc tip: Phng php ny kh thc hin, hn na

tng hp zeolite Y c Si/Al cao hn 33.5 l khng th thc

hin c quy m cng nghip

Cc phng php iu ch zeolite Y c t s

Si/Al cao

X l ha hc: tch Al t zeolite thng thng km theo

cc phn ng gia zeolite vi cc tc nhn ha hc. C
2 trng hp :
Trng hp c th Si vo mng:
Tch nhm vi (NH4)2SiF6
Tch nhm bng SiCl4
Trng hp khng th Si vo mng:
Bng tc nhn selat
Bng cc halogen bay hi
Bng flourin

Cc phng php iu ch zeolite Y c t s

Si/Al cao
X l nhit v nhit hi nc :

Nung zeolite Y trao i vi NH 4+ trong mi trng

hi nc nhit cao
Trong qu trnh tch nhm c th lm ph v mt

phn cu trc ca tinh th zeolite to ra mt s dng

oxyt nhm ,oxyt silic ,aluminosilicate v nh hnh
Kt hp x l nhit v x l ha hc
Phng php ny nhm chuyn zeolite Y dng amoni

(NH4+-Y) thnh dng siu bn bng x l nhit,tip

n x l Al bng phng php ngoi mng.

c. Phng php tng hp

USY
Tng hp USY
o K thut truyn thng s dng nhit cao 1300oF n 1500oF

(704oC n 816oC) dng hi nung zeolit HY

o Lc bng axit, trch li ho hc v thay th ho hc l tt c cc

dng ca tch nhm, dng ph bin trong nhng nm gn y.

o u im chnh ca nhng qu trnh ny so vi tch nhm truyn

thng l vic loi b ca zeolit khng c nhm trong khung hay l

ht gi Al2O3trong lng cu trc zeolit.

S kt tinh, trao i ion v bin tnh cu trc Zeolite Y

(RE: cation ca nguyn t t him)

d. Phng php tng hp

ZSM-5

Qua trnh tao

d. Phng php tng hp

ZSM-5

d. Phng php tng hp

ZSM-5
Template : cht to cu truc

nh hng n qu trnh gel ha v to nhn

tinh th : to ra nhng hnh thi nh trc cho
qu trnh to nhn v tinh th
Lm bn b khung nh cc tng tc lc ht
H, tnh i n
Tng kh nng tng hp c hm lng Si cao

 TMA +

tetramethylammoni
um cations
(TPA+ ) tetrapropyl
ammonium salts
TEA Triethanolamine

d. Phng php tng hp

130 -220 oC
ZSM-5
15- 75 gi
Sol
SiO22

Al2O3
+
Dd
NaOH
Templa
te
+
Mm

pH= 10-10,5

Gel

Lc,Ra
Sy,Nung

NaZSM-5

2.Tng hp Zeolite t hp cht v c c

cu trc
CHUYN HA KAOLIN THNH
Kaolin l mt khong sn phi kim c hnh thnh do qu
ZEOLITE

trnh phong ha ca phenpat ch yu l octodaz v anbit. Qu

trnh phong ha trn c gi l qu trnh kaolin ha.
Ngun kaolin Vit Nam d bo khong 15 triu tn, hm
lng Al2O3 trong kaolin khong t 29% n 50%. Qung
kaolin tp trung ch yu cc tnh nh Lo Cai, Yn Bi, Ph
Th, Qung Ninh, Tuyn Quang, Lm ng, ng Nai
Cng thc ha hc:
Al2O3.2SiO2.2H2O
Thnh phn l thuyt:
SiO2

46,6%

H 2O

13,92%

T trng: 2,57 2,61

cng: 1 -2,5

Al2O3

39,48%

Kaolin bt+NaHCO3
Nghin

30-40

Lm mn
nh hnh
Lm kh
6000C
12-24h

Nung
Tch bi

95-1000C

m 33-34%

CHUYN
m 15-17% HA
KAOLIN
THNH
ZEOLITE

Kt tinh dng quay

Ra
Sy
Zeolite

pH~11,5

CHUYN HA KAOLIN THNH

ZEOLITE

References
Properties, Preparation and Application of

Zeolites(Wolfgang Schmidt , Dr. rer. nat Max-PlanckInstitut fr Kohlenforschung)

http://www.grace.com/EngineeredMaterials/MaterialSciences

/Zeolites/ZeoliteStructure.aspx

www.oilgasportalvn.com
Introduction to zeolite science and practice 3rd revised

edition

Zeolitic Materials: Ion Exchange and Shape Selective-

Catalysis Angus P. Wilkinson-School of Chemistry and

Biochemistry-Georgia Institute of Technology

Catalysist by Metal containing Zeolites( Martin Wallau and

Ulf Schuchardt- Campinas Brazil)

References
Gio trnh xc tc d th (H S Thong)
Nghin cu tng hp zeolite A,X v kho st kh nng s dng
lm kh ru (Lun vn cao hc- GV Nguyn Th Thu Vn)

Atlas of Zeolite Framework types- Fifth revised edition- 2001

Gio trnh k thut xc tc- Thy Mai Hu Khim

ZSM-5 type zeolites:

Synthesis and use in gasphase reactions with ammonia- F.J. van der
Gaag