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 ttrong 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

ng knh S nguyn t O trong Loi zeolite 1 ca s mao qun ( A0 ) 8 ( mao qun hp ) 10 ( mao qun trung bnh ) 12 ( mao qun rng ) 4,3 6,3 8,0 A , Erionit ZSM-5, Ferrierit 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-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 S trung bnh Zeolite giu Si

Phn loi theo thnh phn ha hc

Zeolite ngho Si giu Al Click to edit Master text styles Second level Third level Fourth level Fifth level

Phn loi theo thnh phn ha hc

Zeolite c hm lng Si trung bnh
Click to edit Master text styles Second level Third level Fourth level Fifth level

Phn loi theo thnh phn ha hc

Zeolite giu Si & ry phn t zeolite
Zeolite giu Si

Click to edit Ry phn t zeolite

Master text styles Second level Third level Fourth level Fifth level

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

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

H zeolite aluminophotphat ( AlPO )

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 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 H zeolite aluminophotphat hc

( 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 trc Zeolite tng a. Cu

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 Cu trc s cp Zeolit

1.Tm: Al hay Si 2.nh: O

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

qut:

Cc t din trn lin kt vi nhau qua nguyn t oxy thnh Cu trc th cp

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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

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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

Xc tc mi yu cu

siu bn

USY

tch bt Al ra khi mng to edit Master text sty Click Zeolite, gim hm lng Second level Third level Na trong Zeolite tng Fourth level kh nng to olefin. Fifth level Zeolite siu bn (UltraStable Y : USY). bn cao hn nhiu so vi Zeolite Y truyn thng.

26

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

Cac chui lin kt thanh lp

d. Cu trc ZSM-5

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 S phn b cc tm acid l mt yu t nh hng

c bn n hot tnh v tnh chn lc ca Zeolite. V d : Mt Zeolite c UCS thp t tm acid trn 1 . Cc tm acid t, li cch xa nhau nn trnh c phn ng Chuyn hydro, do lm tng ch s Octane ca xng cng nh tng hiu sut thu sn phm C3 vcc sn phm nh hn.(S tng ch s Octane ny l do nng cao ca Olefin trong xng). Zeolite USY c UCS thp c hot tnh km hn loi REY truyn thng. Tuy nhin, Zeolitec UCS thp c kh nng gi c hot tnh di iu kin hot ng khc nghit ca qu trnh, do cn c gi l UltraStable Y Zeolite mi sn xut c UCS kh cao trong khong 24.5 n 24.75 A. Mi trng nhit v thy nhit trong thit b ti sinh rt cc nhm alumina (AlO2) lm gim UCS.

 ZSM-5 l mt loi

Zeolite c cu trc xp khc vi Y-Zeolite. Kch thc l rng ca ZSM5 nh hn so vi YZeolite (5.1-5.6 so vi 8-9). Thm vo , s sp xp l rng ca ZSM-5 khc so vi Y-zeolite.

4. Tnh cht b mt ca Zeolit

4. Tnh cht b mt ca Zeolit

a. Tnh trao i ion

S oxy ha ca Si:+4, Al:+3 Tm Si trung ha in Tm 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

Khng lm thay i cu trc tinh th v tr khc nhau, tc trao i khc nhau o v tr m(b mt) : d dng o 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) o Phn b ng u cation cc v tr khc nhau o 1phn cation di chuyn t v tr kn m o d trao i

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

Trao i ion hnh thnh tm axit Qu trnh hnh thnh tm axit:

Tm bronsted

T0C

Tm Lewis

Click to edit Master text styles Cc ion nh Na+,Mg2+ hay proto Second level Third level n s trung ho in Fourth level tch ny v hnh Fifth level 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 hnh thnh cc tm axit b. S

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 chn lc hnh hc c. Tnh

4. ng dng ca Zeolit

Cc qu trnh tch

Lm cht xc tc

Trong ha phn tc

Lm cht trao i ion

4. ng dng ca Zeolit

Tch C2H2 ra khi butadien, khng kh lng

ng dng cho cc qu trnh tch

Tch NO ra khi kh v cht lng Lm kh cc cht lng v hi Tch hi du khi kh nn Tch CO khi He v H2

4. ng dng ca Zeolit

D ng tro ch t AgA ng h ch m lm n u kh n g
Ha phn tch

m Phn tch

h tc n h k t p c c s ph m ng p L tro h kh

4. ng dng ca Zeolit

Nhng cation kim loi c th b tch ra

o i ion

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,eh ydro, ehydrat ( USY dng trong FCC ) Fe-ZSM-5 : xuc tac cho phan ng

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 MCU-4,3

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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.

 Co nhieu nh ngha va nhan nh khac nhau : Morey & Niggli (1913) ,

Phn ng thu nhit l g?

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 Qu trnh lm mui Qu trnh kt tinh Qu trnh lc ra

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 aluminate phn 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

Pha lng

phn ng a t
Hnh thnh mm tinh th

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

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 m Lm mui Lc H2O thi

H2O NaAlO2

H2O

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: t0 phng Phng php 2: t0 kt tinh khuy u Al(OH)3 Na2SiO3

Na2SiO3

NaOH

H2O NaAlO2 To gel NaAlO NaOH 2 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

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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 Tch dd thu kt ta hydro Aluminosilicat Loi kim d

NaAlO2 Na2O.nH2O TB phn ng TB kt tinh Lc khung bn Ra Nghin

Kt tinh
Zeolite X: 95-100oC trong 12h Zeolite Y: 990C trong 10h. pH 10,5

Zeolite A: 80-90oC trong 6h

m 35% 120-150oC Loi bi

To vin Sy Sng quay L nung zeolite

30-40 ph m 35%

Tng hp zeolite loi X,Y

575-6500C 624h Dng tinh th

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Second level

Third level

Fourth level Fifth level

c. Phng php tng hp USY

v

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

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:

Cc phng php iu ch zeolite Y c t s Si/Al cao

v

Tch nhm vi (NH4)2SiF6 Tch nhm bng SiCl4 Bng tc nhn selat Bng cc halogen bay hi Bng flourin

Trng hp khng th Si vo mng:

Cc phng php iu ch zeolite Y c t s Si/Al cao

v

X l nhit v nhit hi nc :

Nung zeolite Y trao i vi NH4+ 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.

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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

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Qua trnh tao gel

d. Phng php tng hp ZSM-5

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d. Phng php tng hp ZSM-5 Template : cht tao cu truc

Anh hng n qua trinh gel hoa va tao nhn tinh th : tao ra nhng hinh thai inh trc cho qua trinh tao nhn va tinh th

Lam bn b khung nh cac tng tac lc hut H, tinh in

Tng kha nng tng hp co ham lng Si cao

 TMA +

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

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d. Phng php tng hp ZSM-5

130 -220 oC 15- 75 gi pH= 10-10,5

Sol SiO2

Al2O3 + Dd NaOH Templa te + Mm

Gel

NaZSM-5

Lc,Ra

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 trnh ZEOLITE
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: Al2O3 39,48%

SiO2 H2O T trng: cng: 46,6% 13,92% 2,57 2,61 1 -2,5

Kaolin bt+NaHCO3 Nghin Lm mn nh hnh Lm kh 6000C 12-24h 95-1000C Nung Tch bi Ra Sy Zeolite m 33-34% 30-40

CHUYN m 15-17% HA KAOLIN THNH ZEOLITE

pH~11,5

Kt tinh dng quay

CHUYN HA KAOLIN THNH ZEOLITE Click to edit Master text styles

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References
Properties, Preparation and Application of

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

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

Catalysist by Metal containing Zeolites( Martin Wallau and

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