tai lieu ve zeolit

8/3/2019 Tai Lieu Ve Zeolit

1/98

I/ Gii thiu v Zeolite

Theo ting Hy Lp Zeo: si, Lithot: , v vy zeolite cngha 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 v10.000 pht minh sng kin tng hp zeolite.Nh vy zeolite c tm quan trng ln lao trong khoa hc vk thut.

1/ Ngun gc- nh ngha:


2/98

Zeolite qua knh hin vi in t-trong t nhin


3/98

Phn loi

Theokch thcmao qun

Theo

thnh phnha hc

2/ Phn loi


4/98

mao qunrng

7 8 A0

mao qun trungbnh

5 6,9 A0

mao qun hp

< 5 A0

S nguyn t O trong1 ca s

ng knhmao qun ( A0 )

Loi zeolite

8 ( mao qun hp ) 4,3 A , Erionit

10 ( mao qun trungbnh ) 6,3 ZSM-5, Ferrierit

12 ( mao qun rng ) 8,0 X, Y, Mordenit

Phn loi da theo kch thcmao qun


5/98

Phn loi theo thnh phn hahcTheo 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 ticc 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

TPHH

Zeolite ngho Si giu AlH zeolite

anuminophotphat

Zeolite c hm lngtrung bnh

Zeolite giu Si

Zeolite giu Si tch Al

Ry phn t zeolite


6/98

Click to edit Master text stylesSecond level

Third level Fourth level

Fifth level

Phn loi theo thnh phn hahc

Zeolite ngho Si giu Al


7/98



Fifth level

Zeolite c hm lng Si trung bnh



8/98

Zeolite giu Si & ry phn tzeolite

Click to edit Master text stylesSecond levelThird level

Fourth level Fifth level

Zeolite giu Si

Ry phn t zeolite



9/98

Zeolite giu Si tch nhm

Bng cc phng php sau tng hp , ngi ta c th bini thnh phn ha hc ca zeolite. Mt s phn ng ha hcc 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 cgi 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 tl Si/Al 9. vi phng php ny nu zeolite thu c c t lSi/Al > 9 th s ph v mng li tinh th ca zeolite.



10/98

H zeolite aluminophotphat( AlPO )

Gn y c mt h cht rn mi c cu trc tinh th tng t zeolit gi lAluminophotphat (AlPO) c pht minh bi cc nh nghin cu ca Linhip 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 tot 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 hFaujazit 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 cacacbon b tr, khng c kh nng trao i cation v v vy khng c tnh xctc.



11/98

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 ication.

MeAPO: nu a cc nguyn t khc nh Co, Mn, Fe, V, Ga... voSAPO 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 cutrc hnh hc cc vt liu Co-APO, Mn-APO, V-APO c cu trc tngt AlPO5, AlPO11, AlPO17, AlPO31.

H zeolite aluminophotphat( AlPO )



12/98

3. Cc loi Cu trc

Zeolita. Cu trc Zeolite tng qutb. Cu trc Zeolit A, X, Yc. Cu trc ZSM5d. Cu trc USY

Ngoi ra cn c zeolite aluminophotphat cu tot cc t din AlO4- v PO4+ nh AlPO-5

(ging Zeolite X,Y) ALPO-11(ging ZSM5).


13/98

a. Cu trc Zeolite tngqut: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


14/98

Cu trc s cp



Fifth level

1.Tm: Al hay Si2.nh: O

3. Cc loi Cu trcZeolit


15/98

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

a. Cu trc Zeolite tngqut:

3. Cc loi Cu trcZeolit


16/98



Fifth level


17/98

b. Cu trc Zeolit A, X,Y

Cu trc th cp: hnh bt din ctgm :

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


18/98

Cu trc Zeolit A(LTA)

Cc soalit ghp ni

vi nhau ti cc mt4cnh thng qua trunggian lng tr to thnhZeolite A

b. Cu trc Zeolit A, X,Y


19/98


Third level



20/98

Cu trc Zeolit A (LTA)b. Cu trc Zeolit A, X,Y


21/98

LTA


22/98

LTA


23/98

Cu trc Zeolit X,Y

Sodalit ghp vi nhau ti ccmt 6cnh thnh Zeolite X,Y

kch thc l Zeolite A< X,Y

T l Si/Al ca Zeolit X


24/98

Cu trc Zeolite Xb. Cu trc Zeolit A, X,Y


25/98

FAU


26/98

Zeolite siu bn

USYXc tc mi yu cutch bt Al ra khi mngZeolite, gim hm lng

Na trong Zeolite tngkh nng to olefin.Zeolite siu bn

(UltraStable Y : USY). bn cao hn nhiu

so vi Zeolite Y truynthng.

26

Click to edit Master text stSecond level

Third level Fourth level Fifth leve

c. Cu trc USY


27/98

Cu trc th cp:12 t din SiO4/2 vAlO4/2 ghp vi nhaunh hnh bn to

d. Cu trc ZSM-5


28/98

Cc chuilin ktthnh lp

d. Cu trc ZSM-5


29/98

d. Cu trc ZSM-5

Click to edit Master text styles


30/98



Fifth level


31/98


32/98


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S phn b cc tm acid l mt yu t nh hngc bn n hot tnh v tnh chn lc ca Zeolite.

V d : Mt Zeolite c UCS thp t tm acid trn1 . Cc tm acid t, li cch xa nhau nn trnhc phn ng Chuyn hydro, do lm tng chs Octane ca xng cng nh tng hiu sut thusn phm C3 vcc sn phm nh hn.(S tng

ch s Octane ny l do nng cao ca Olefintrong xng).Zeolite USY c UCS thp c hot tnh km hn loi

REY truyn thng. Tuy nhin, Zeolitec UCS thpc kh nng gi c hot tnh di iu kin

hot ng khc nghit ca qu trnh, do cnc gi l UltraStable YZeolite mi sn xut c UCS kh cao trong

khong 24.5 n 24.75 A. Mi trng nhit vthy nhit trong thit b ti sinh rt cc nhmalumina (AlO2) lm gim UCS.


34/98

ZSM-5 l mt loiZeolite c cu trc xpkhc vi Y-Zeolite. Kch

thc l rng ca ZSM-5 nh hn so vi Y-Zeolite (5.1-5.6 so vi8-9).

Thm vo , s spxp l rng ca ZSM-5khc so vi Y-zeolite.


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4. Tnh cht b mt caZeolit

4 Tnh cht b mt ca


36/98

a. Tnh trao i ion

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

Tm Si trung ha in

Tm Al t ch in m trung ha bi 1iondng( ion kim hoc kim th) trao i ion

4. Tnh cht b mt caZeolit


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a. Tnh trao i ion


38/98

Khng lm thay i cu trctinh th

v tr khc nhau, tc traoi khc nhauov tr m(b mt) : d dngo v tr kn (soalit, lng tr):

kh khn

a. Tnh trao i ion


39/98

tng trao i ion:o x l vi dd cha ion trao i nhiu ln

o Gia cc ln phi sy kh v x lnhit(nung 5000C)o Phn b ng u cation cc v tr khc

nhau

o 1phn cation di chuyn t v tr kn mo d trao i

a. Tnh trao i ion


40/98

Trao i ion hnh thnh tm axit

Qu trnh hnh thnh tm axit:

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


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T0C

TmLewis

Cli k t dit M t t t t l


43/98



Fifth level

Khi tin hnh x l nhit khong nhit 400 500oC th xut hin cc tmaxt Lewis theo s sau:

Cc ion nhNa+,Mg2+ hay proton s trung ho in

tch ny v hnhthnh tm axitBronsted

4 T h h b


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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 cacc proton khc nhau axit khngng u.

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

4 Tnh cht b mt ca


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4. Tnh cht b mt caZeolitc. Tnh chn lc hnh hc


46/98

4 d Z lit


47/98

Trong ha phn tLm cht xc tc

Cc qu trnh tch

Lm cht trao i ion

4. ng dng ca Zeolit

4 d Z lit


48/98

Tch C2H2 ra khi butadien,khng kh lng

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

ng dng chocc qu trnh

tch

4. ng dng ca Zeolit

4 d Z lit


49/98

Dng

AgA

lm

chth

mu

tron

gchn

khn

g

Lmctp

hntch

trongsck

khhpph

Phntch

m

Haphntch

4. ng dng ca Zeolit

4 d Z lit


50/98

o i ion

Nhng cation kim loi c th b tch rakhi 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 nhnc ngt khi gp nn bin

4. ng dng ca Zeolit

4 d Z lit


51/98

Lm cht xc

tc

Lm cht xctc cho phnng ng phnha C5, C6

nhm nng caoch s octan

Lm cht xctc cho qutrnhCracking,ehydro,ehydrat( USY dngtrong FCC )Fe-ZSM-5 :

xc tc chohn n

Dng lm chtmang cho cc

loi xc tckhc.

4. ng dng ca Zeolit


52/98


53/98


54/98

Gas separation membrane using zeolite


55/98

Zeolite Gas-Pump With No MovingParts, But With A High Rate Of Gas

Flow


56/98

Dr Peter Maier-Laxhuber & Zeolite Cooler


57/98

Dr. Peter Maier-Laxhuber, et al.


58/98

Zeolite Heat

Pump withIntegrated Ice-Storage


59/98

Oil Purification

Zeolite StationMCU-4,3

Click to edit Master text stylesS d l l


60/98

Second level Third level

Fourth level

Fifth level

II/ T NG HP ZEOLITE


61/98

II/ T NG HP ZEOLITE

Zeolite l cc aluminosilicat ngm nc,c hnh thnh di cc iu kin thunhitNgha l mt h lng, cha cc thnhphn ho hc thch hp c kt tinh

di tc dng ca nhit.

1. Nguyn tc chung

Ph h hi l


62/98

Phn ng thu nhit lg?

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 matcua dung moi (nc hoac khong phai la nc) dien ra tai nhiet oln 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 ocan at ti lai qua cao khien cho pha long khong ton tai c nenphai 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 suatcao va nhiet o cao goi la autoclave


63/98

ieu kien tonghp Zeolite

Nguyn liu u: hot tnh cao

pH mi trng: kh kimNhit : thpp sut: thc hin p sut hi bo ha ca ncMc qu bo ha ca dung dch kt tinh phi

ph hp khng qu ln cng khng qu b.

1. Nguyn tc chung


64/98

Qu trnh to gel

Qu trnh lm mui

Qu trnh kt tinh

Qu trnh lc ra

Qu trnh kt tinh Zeolite gm cc giai on:


65/98

Qu trnh to gel: quan trng nhto Ch xy ra trong dung dch, mi trng kim mnho Ch to thnh trong khong gii hn t l Si/Al thch hpo Hnh thnh lin kt Si-O-Al trong khung gel do tng tc ca dd silicat v

aluminate phn ng a trng ngng:


66/98

Qu trnh lm mui: cn thit cho tomm tinh th

o Mm tinh th bt u hnh thnh trong phalng 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


67/98

Pha rn v nh hnh Pha lng

Gel aluminosilicate ban u

Pha rnv nh hnh

Kt tinh gel Pha lng

Hnh thnhmm tinh th

Kt t li thnhtinh th zeolite

un nng

t0C ha tan lm nng tng phn na t

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

SN PHM KT TINH

QU TRNH KT TINH ZEOLITE


68/98

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

tinh th. Cng sch kim, cht lngZeolite cng cao

oThc t, pH nc ra cn khong 8-9 lt yu cu.


69/98


70/98

Trong cc yu t nh hng qu trnh kt tinh, bncht v tnh cht zeolite, thnh phn gel ban u l quan

trng nht.

Cc yu t

nhhngn qutrnh tng

hpZeolite

Na2SiO3 NaOH Al(OH)3


71/98

Na2SiO3 NaOH Al(OH)3

NaAlO2

H2O

H2O

To gel

Lm mui

Kt tinh

Lc

H2O thi

H2O m

Sn phm

S QUY TRNH TNG HP ZEOLITE

2.Tng hp Zeolite t hp cht v ckh t


72/98

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- 2,2Na2O/SiO2 = 1,7- 2,8

[Na2O] =0.33- 0.92 mol/l

a. Phng php tng hp

zeolite A

g p pkhng c cu trc

a Phng php tng hp


73/98

Phng php 1:To gel aluminosilicat t thy tinh lng hay tinh th natri silicattrn 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 natrialuminat trong kim nhit kt tinh v khuy u.

Tinh th Zeolite thu c trng hp ny c kch thc lnhn cch tng hp theo phng php 1.

a. Phng php tng hpzeolite A

a. Phng php tng hp


74/98

Na2SiO3

NaOHNaAlO2

t0 kt tinh

khuy u

To gel

Phng php 2:

a2SiO3 NaOH Al(OH)3

NaAlO2

H2O

To gel

t0 phng

Phng php 1:


a Phng php tng hp


75/98

Cc yu t nh hng

Nhit : tng hp p sut thng th khong nhit dao ng khrng.

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, nhngnng thp th kh kt tinh c gel aluminosilicat.

Hm lng nc: nh hng n qu trnh to gel ban u, hm lngnc cng cao th trng kt tinh ca NaA cng rng


a. Phng php tng hp


76/98



Fifth level


b Phng php tng hp zeolite


77/98

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 =25-65Thnh phn gel tng hp Zeolite Y: SiO2/Al2O3 = 8 Na2O/SiO2 = 0.4 H2O/Na2O =10

b. Phng php tng hp zeoliteX,Y

NaAlO2 Kt tinhDd c khuytrn kt t


78/98

TB phn ng

TB kt tinh

Lc khung bn

Ra

Nghin

To vin

Sy

Sng quay

L nung

zeolite

Na2O.nH2O

Loi kim d

m 35%

120-150oC

Loi bi

Dng tinh th

30-40 ph m 35%

Zeolite A: 80-90oC trong 6

Zeolite X: 95-100oC trong12hZeolite Y: 990C trong10h. pH 10,5

Tch dd thu kt tahydro Aluminosilicat

trn, kt tthnh ta gel xpAluminosilicat

575-6500C624h

Tng hpzeolite loiX,Y


79/98


Second level Third level Fourth level

Fifth level

c. Phng php tng hp


80/98

vCc phng php iu ch zeolite Y c t

s Si/Al caoTng 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 hcKt hp x l thy nhit v x l ha hc

Tng hp trc tip: Phng php ny kh thc hin, hn na tnghp zeolite Y c Si/Al cao hn 33.5 l khng th thc hin c quy m cng nghip

g p p g pUSY

vCc phng php iu ch zeolite Y c t sSi/Al cao


81/98

X l ha hc: tch Al t zeolite thng thng km theocc phn ng gia zeolite vi cc tc nhn ha hc. C2 trng hp :

Trng hp c th Si vo mng:

Tch nhm vi (NH4)2SiF6

Tch nhm bng SiCl4Trng hp khng th Si vo mng:

Bng tc nhn selat

Bng cc halogen bay hi Bng flourin

Si/Al cao

vCc phng php iu ch zeolite Y c t s


82/98

X l nhit v nhit hi nc :

Nung zeolite Y trao i vi NH4+ trong mitrng hi nc nhit cao

Trong qu trnh tch nhm c th lm ph v mtphn cu trc ca tinh th zeolite to ra mt s

dng oxyt nhm ,oxyt silic ,aluminosilicate v nhhnh

Kt hp x l nhit v x l ha hcPhng php ny nhm chuyn zeolite Y dng

amoni (NH4+-Y) thnh dng siu bn bng x lnhit,tip n x l Al bng phng php ngoimng.

vCc phng php iu ch zeolite Y c t sSi/Al cao

c. Phng php tng hp


83/98

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 ccdng 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 lht gi Al2O3trong lng cu trc zeolit.

g gUSY



84/98


Fifth level


85/98

S kt tinh, trao i ion v bin tnh cu trc Zeolite Y(RE: cation ca nguyn t t him)

d Ph h h


86/98

Qua trnh tao

el


Third level


d. Phng php tng hpZSM-5

d Ph h t h


87/98



Fifth level

d. Phng php tng hpZSM-5

d. Phng php tng hpZSM 5


88/98

Template : cht to cu truc

nh hng n qu trnh gel ha v to nhntinh 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

ZSM-5


89/98

TMA +tetramethylammonium cations

(TPA+ ) tetrapropylammonium saltsTEA Triethanolamine


90/98


91/98


92/98

d. Phng php tng hpZSM 5


93/98

SolSiO2

Al2O3+

DdNaOH

Template+

Mm

Gel

130 -220 oC

15- 75 gipH= 10-10,5

Lc,Ra

NaZSM-5

ZSM-5

2.Tng hp Zeolite t hp cht v c ccu trc


94/98

Kaolin l mt khong sn phi kim c hnh thnh do qu trnhphong ha ca phenpat ch yu l octodaz v anbit. Qu trnhphong ha trn c gi l qu trnh kaolin ha.

Ngun kaolin Vit Nam d bo khong 15 triu tn, hmlng Al2O3 trong kaolin khong t 29% n 50%. Qungkaolin 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 46,6%

H2O 13,92%

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

CHUYN HA KAOLIN THNHZEOLITE

cu trc

Kaolin bt+NaHCO3


95/98

Nghin

Lm mn

nh hnh

Lm kh

NungTch bi

Kt tinh dng quay

RaSy

Zeolite

30-40

m 33-34%

m 15-17%

6000C12-24h

95-1000C

pH~11,5

CHUYNHAKAOLINTHNHZEOLITE

CHUYN HA KAOLIN THNH


96/98


Second levelThird level Fourth level

Fifth level

CHUYN HA KAOLIN THNHZEOLITE

References


97/98

References Properties, Preparation and Application of

Zeolites (Wolfgang Schmidt , Dr. rer. natMax-Planck-Institut fr Kohlenforschung)

http://www.grace.com/EngineeredMaterials/MaterialSciences/Zeolites/ZeoliteStructure.aspx

www.oilgasportalvn.com

Introduction to zeolite science and practice 3rd revisededition

Zeolitic Materials: Ion Exchange and Shape Selective-

Catalysis Angus P. Wilkinson-School of Chemistry andBiochemistry-Georgia Institute of Technology

Catalysist by Metal containing Zeolites( Martin Wallau andUlf Schuchardt- Campinas Brazil)

References
http://www.oilgasportalvn.com/http://www.oilgasportalvn.com/


98/98

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 derGaag

References

tai lieu ve zeolit

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