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

mao qun hp
< 5 A0

S nguyn t O trong 1 ca s 8 ( mao qun hp ) 10 ( mao qun trung bnh ) 12 ( mao qun rng )

ng knh mao qun ( A0 ) 4,3 6,3 8,0

Loi zeolite A , Erionit ZSM-5, Ferrierit X, Y, Mordenit

Phn loi theo thnh phn ha hc

Theo quy tc Loweinstein xc nh rng : 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-O-Si Ni cch khc ch tn ti loi t l Si/Al 1

H zeolite anuminophotphat

Zeolite ngho Si giu Al

Zeolite giu Si tch Al Ry phn t zeolite

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 hc

H zeolite aluminophotphat ( 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 SiO4 v AlO4m 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

Cu trc Zeolite tng qut Cu trc Zeolit A, X, Y Cu trc ZSM5 Cu trc USY

a. b. c. d.

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 USY

Xc tc mi yu cu 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 Khng lm thay i cu trc tinh th o 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
Dng lm cht mang cho cc loi xc tc khc.

Lm cht xc

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

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 hoa hp cht thm

 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 Ice-Storage

 Oil Purification

Zeolite Station MCU-4,3

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 b~o ha ca nc

Mc qu| b~o 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 o o

Ch xy ra trong dung dch, mi trng kim mnh Ch to th{nh trong khong gii hn t l Si/Al thch hp Hnh th{nh lin kt Si-O-Al trong khung gel do tng t|c ca dd silicat v{ aluminatephn ng a trng ngng:

 Qu| trnh l{m mui: cn thit cho to mm tinh

th
o Mm tinh th bt u hnh th{nh trong pha lng ca

gel hoc ti b mt ph}n c|ch pha ( gel-dd)

o Khi cu trc tinh th c to t c|c 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

Pha lng
phn ng a t

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

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 c|c xoang tinh th.

C{ng sch kim, cht lng Zeolite c{ng 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 m Lm mui

Lc

H2O
NaAlO2

H2O

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
C|c Zeolite t nhin c tinh ch, loi b tp cht. C|c ngun nguyn liu t nhin: kaolin, t st ~ c

bin tnh bng ha cht

Th{nh 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 c|ch 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 c|ch rt dung dch natri silicat v{o natri aluminat trong kim nhit kt tinh v{ khuy u. Tinh th Zeolite thu c trng hp n{y c kch thc ln hn c|ch tng hp theo phng ph|p 1.

a. Phng php tng hp zeolite A

Phng php 1:
t0 phng

Phng php 2:
t0 kt tinh khuy u

Na2SiO3

NaOH

Al(OH)3

Na2SiO3

H2O NaAlO2

NaAlO2

NaOH

To gel

To gel

a. Phng php tng hp zeolite A

C|c 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 d{i, nhng nng thp th kh kt tinh c gel aluminosilicat. Hm lng nc: nh hng n qu| trnh to gel ban u, h{m lng nc c{ng cao th trng kt tinh ca NaA c{ng 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 H2O/Na2O =10

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

NaAlO2

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

Na2O.nH2O TB phn ng
TB kt tinh

Zeolite X: 95-100oC trong 12h

Tch dd thu kt ta hydro Aluminosilicat Lc khung bn

Loi kim d Ra

Zeolite Y: 990C trong 10h. pH 10,5

30-40 ph m 35%

Nghin
m 35% 120-150oC Loi bi To vin Sy Sng quay L nung

Tng hp zeolite loi X,Y

575-6500C 624h Dng tinh th

zeolite

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 ph|p 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 ph|p n{y 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 hoa 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 NH4+ trong mi trng

hi nc nhit cao
Trong qu| trnh t|ch nhm c th l{m 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 ph|p n{y nhm chuyn zeolite Y dng amoni

(NH4+-Y) th{nh dng siu bn bng x l nhit,tip n x l Al bng phng ph|p ngo{i 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 gel

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 in Tng kh nng tng hp c hm lng Si cao

 TMA +

tetramethylammonium cations (TPA+ ) tetrapropyl ammonium salts TEA Triethanolamine

d. Phng php tng hp ZSM-5

130 -220 oC
15- 75 gi Sol SiO2
Al2O3 + Dd NaOH
Templat e + 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 ZEOLITE

Kaolin l{ mt kho|ng sn phi kim c hnh th{nh do qu|

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 b|o khong 15 triu tn, h{m lng Al2O3 trong kaolin khong t 29% n 50%. Qung kaolin tp trung ch yu c|c tnh nh L{o Cai, Yn B|i, Ph Th, Qung Ninh, Tuyn Quang, L}m ng, ng Nai

Cng thc ha hc: Th{nh phn l thuyt:

Al2O3.2SiO2.2H2O
Al2O3 SiO2 H2O 39,48% 46,6% 13,92%

T trng: 2,57 2,61 cng: 1 -2,5

Kaolin bt+NaHCO3 Nghin Lm mn 30-40

nh hnh
Lm kh 6000C 12-24h 95-1000C Nung Tch bi

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-Planck-Institut fr Kohlenforschung) ZeoliteStructure.aspx

http://www.grace.com/EngineeredMaterials/MaterialSciences/Zeolites/
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 Schuchardt- Campinas Brazil)

Catalysist by Metal containing Zeolites( Martin Wallau and Ulf

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

Gi|o trnh k thut xc t|c- Thy Mai Hu Khim

ZSM-5 type zeolites:

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