M U.............................................................................................................................

2
CHNG I : TNG QUAN L THUYT....................................................................4
I.1. NHM HYDROXYT..............................................................................................4
I.1.1. S phn hy nhit ca cc dng nhm hydroxyt..........................................4
I.1.2. Cu trc v tnh cht ca Beomite.................................................................5
I.2. CU TRC V TNH CHT CA -AL2O3:.....................................................8
I.2.1. Cu trc ca -Al2O3:......................................................................................8
I.2.2. Tnh cht b mt ca -Al2O3:.......................................................................11
I.2.3. Cu trc xp ca -Al2O3:.............................................................................11
I.3. VT LIU MESOPOROUS V MESOPOROUS -Al2O3..............................13
I.3.1. Gii thiu chung v vt liu MQTB..............................................................13
I.3.2 Phn loi vt liu MQTB................................................................................15
I.3.3. Cc dng ng ng nhit hp ph v nh hp ph ca vt liu MQTB
...................................................................................................................................15
I.3.4. Thnh phn tng hp vt liu MQTB..........................................................17
I.3.5. C ch hnh thnh cu trc vt liu MQTB................................................18
I.4. ng dng ca nhm oxit.....................................................................................25
I.4.1. ng dng ca Al2O3 ni chung.....................................................................25
I.4.2. ng dng ca - Al2O3.................................................................................27
I.4.3. Trin vng pht trin sn xut -Al2O3.......................................................28
CHNG II : THC NGHIM....................................................................................30
II.1. DNG C V HO CHT TH NGHIM.....................................................30
II.1.1. Ho cht th nghim :...................................................................................30
II.1.2. Dng c th nghim:.....................................................................................30
II.2. QUY TRNH THC NGHIM..........................................................................31
II.3. CC PHNG PHP NGHIN CU C TRNG CA VT LIU......32
II.3.1. Nghin cu nh tnh pha tinh th bng nhiu x Rnghen.....................33
II.3.2. Phng php xc nh b mt ring v phn b l xp ca cht mang v
xc tc bng phng php BET.............................................................................34
II.3.3. Phng php phn tch nhit......................................................................37
II.3.4. Phng php hin vi in t truyn qua TEM..........................................38
II.3.5. Hin vi in t qut (SEM)..........................................................................39
CHNG III : KT QU V THO LUN..............................................................40
III.1. HYDROXIT NHM DNG BOEMITE.........................................................40
III.1.1. nh hng cu ch gi ho...................................................................40
III.1.2. Kho st bin i ca Beomite theo nhit ............................................44
III.2. VT LIU MQTB -Al2O3................................................................................47
III.2.1.. nh hng cu ch nung......................................................................47
III.2.1.. nh hng cu tc nung......................................................................50

M U
Trc y, vt liu vi mao qun Zeolit rt c quan tm v kh nng ng
dng trong cc lnh vc nh xc tc, ha du, tng hp hu c v bo v mi
trng. Do Zeolite c h thng vi mao qun ng u thnh phn ha hc a dng.
Tuy nhin zeolit cn tn ti mt s hn ch sau: khng th xc tc nu phn t
cht tham gia phn ng c kch thc ln hn kch thc vi mao qun.
Chnh v vy vic tng hp vt liu c kch thc mao qun trung bnh
v ang thu ht nhiu s quan tm ca cc nh khoa hc. Vo thp k 90, cc
thnh cng trong vic t hp cc vt liu mao qun trung bnh (MQTB) m ra
mt trin vng to ln trong tng hp cht xc tc v hp ph. Cc vt liu ny c
b mt ring ln, kch thc mao qun ln (2 - 50 nm), cu trc mao qun vi
trt t cao, ng u. Chng cho php cc phn t ln c th d dng khuch tn
v tham gia phn ng bn trong mao qun.
Trong cc nh my lc ho du, nguyn liu u vo l du th cha rt
nhiu thnh phn nn cn phi phn tch hay chuyn i chng theo cc qu trnh
ho hc phc v cho cc mc ch khc nhau. Vic s dng vt liu mao qun
trung bnh trong hp ph tch cc cu t cn thit nh n-parafin, cc hp cht
vng thm nhm: lm tng tr s octan ca xng, tng phm cht ca nhin liu,
hay lm nguyn liu u vo cho mt s cc qu trnh tng hp ho hc khc.
Lm cht mang, lm xc tc cho cc qu trnh nh: isome ho, ng phn ho,
refoming, cracking,...
Nhm oxit mao qun trung bnh l mt trong nhng loi vt liu MQTB rt
nhiu ng dng. Ngy nay trn th gii cng nh Vit Nam ang nghin cu v
sn xut cc dng nhm oxit m quan trng nht l -Al2O3 c cu trc xp, b
mt ring ln, c cc tm axit, d to vin, c bn c, bn nhit, chu c

nc chng c dng lm cht ht m trong ch bin kh thin nhin, cht hp

ph, cht mang, xc tc cho ngnh tng hp v c v hu c.
Trong phm vi n ny, chng ti tin hnh tng hp vt liu -Al2O3
MQTB theo phng php s dng Beomit lm tin cht v c v axit cacboxylic
lm cht nh hng cu trc. y l mt phng php n gin v kinh t da.
Ni dung nghin cu chnh l kho st la chn loi axit cacboxylic thch hp
nht; tm ra cc iu kin ti u ch to vt liu -Al2O3 MQTB vi din tch b
ring mt ln v s phn b mao qun hp.

CHNG I : TNG QUAN L THUYT

I.1. NHM HYDROXYT
Nhm hydroxit c chia theo cu trc gm 2 loi:
Nhm tri hydroxit Al(OH)3
Nhm mono hydroxit AlO(OH)
Trong nhm tri hydroxit c 3 dng th hnh : Gibbsit, Bayerit,
Nordstrandit. Cn mono hydroxyt c 2 dng th hnh l Beomite v Diaspor
I.1.1. S phn hy nhit ca cc dng nhm hydroxyt

Gibbsit

Chi

Kappa

Bemit

Gamma

Bayerit

Eta

200

Theta Alpha

Theta

Diaspore

100

Delta

Alpha

Alpha

Alpha

300

400

500

600

700

800

900

1000

1100 0C

Hnh 1: S phn hu nhit ca nhm hydroxit

Qua gin v s phn hu nhit ca nhm hydroxyt ta thy khi nung
Gibbsit qua c 2 giai on:

 Khi nung n 2300C th 2 phn t nc tch ra khi tinh th Gibbsit v

Gibbsit chuyn ho thnh Bemit
Nung n 5000C th phn t nc cui cng b tch ra v Bemit chuyn ho
thnh cc dng nhm oxit.Ti cc nhit khc nhau th lng nc tch ra
khc nhau.
Lc u khi nung 180200oC mt phn nc cu trc b tch ra ko theo
s sp xp li mng li tinh th, lm xut hin bn trong tinh th v trn b mt
ca chng nhng l trng. Khi c s kh nc ca Gibbist bn trong tinh th to
ra mt p sut hi nc cao to iu kin cho vic chuyn ha thnh beomite. Nu
tip tc nung th p sut hi nc tng, qu gii hn th tinh th b ph v.
Qu trnh tch nc ca Gibbsit cho sn phm khc vi Bayerit v
Nordstandit.Trong chn khng, nhit thp 3 dng ca nhm tri hydroxit phn
hu to sn phm v nh hnh,sau nhit cao hn bin i thnh
Al2O3, Al2O3, v Al2O3. Diaspor l nhm hydroxit duy nht phn hu trc
tip ra Al2O3
T gin ta thy ti nhit thp ch c Beomite khi nung mi to ra
c -Al2O3. Cn cc dng nhm hydroxyt khc khi nung cc iu kin nhit
khc nhau to ra cc dng oxit nhm khc nh - Al2O3, - Al2O3, - Al2O3;Al2O3;- Al2O3 v - Al2O3. Chnh v vy ta s ch nghin cu tnh cht v cu trc
ca Beomite v -Al2O3
I.1.2. Cu trc v tnh cht ca Beomite
A. Tinh th beomite
Beomite c cng thc ha hc Al2O3.H2O = 2. AlOOH. Cu trc ca tinh
th beomite gm c 2 lp, cc lp l nhng chui c hnh thnh t cc phn t
AlOOH ( Ewing 1935, Reichert 1946, Mc Atec 1956)

Hnh 2 Cu trc tinh th ca Beomite

Hai lp ny lin kt vi nhau thng qua hydrogen v ion hydroxyl, khong
cch gia O-O l 0,27 nm. Trong tinh th c cc mng c s c hnh thnh t
2 phn t AlOOH vi kch thc
a = 3,6936 + 0,0003 Ao
b = 12,214 + 0,0001 Ao
c = 2,8679 + 0,0003 Ao
Khong cch ca cc nguyn t c trch trong bng di

Trong cc khong cch c o bi RY = Reichertz and Yost (1946), MM =

Milligan and McAtee (1956), BJ = Bezjak and Jelenic (1964)
Trong c s ion Al3+ c bao bc bi 4 oxi v 2 nhm hydroxyl OH to
thnh cc hnh bt din. Trong cu trc c 2 loi oxi in hnh, mt dng l cc
nguyn t oxi c sp xp gia cc lp v n chia thnh 4 hnh bt din, dng
cn li l cc nguyn t c sp xp bn ngoi cc lp n ch chia thnh 2 hnh
bt din.
Mi nguyn t oxi in hnh pha trc s c ni vi hydro bi 2 lin kt
cng ging nh cc nguyn t oxi cc lp k bn. Cng c nhiu gi thit v v
tr ca hydro, c kin cho rng v tr hydro khng nm i xng gia 2 lin kt
ca ion oxy
B. Gel beomite v gi beomite
Khi gi ha ti nhit thp hn 70 oC th gi beomite chuyn thnh dng
tinh th, quan st qu trnh ny ngi ta thy gi beomite l giai on chuyn tip
trong qu trnh gi ha. ( Calvet Introduced the term pseudobeomite 1953 )
Lippens (1961) kt lun rng gel c cc chui l cc phn t (AlOOH) 2
c ni vi nhau qua 2 cu hydrogen thng qua phn t nc. cn Tehen Horst
v Hoff mann 1980 c nhng nghin cu k v a ra kt lun gi beomite l
cc lp tm mt n gin, cha nhiu nc hn beomite thng thng v chng
nm gia cc lp tm mt . Nc c th lin kt vi oxy v hydro trong cu trc
ca chui, v th c th lm tng kch thc ca cc mng

Gi beomite c cng thc ha hc di dng Al 2O3. xH2O trong 1<x<2.

N cha ti trn 30% nc tng ng vi dng AlOOH. Lng nc trong cu
trc khng ch tn ti dng phn t t do m cn lin kt chc chn vi nhau
bng lin kt hydro trong khong gia cc mng.
7

I.2. CU TRC V TNH CHT CA -AL2O3:

Trc khi cp n vt liu -Al2O3 MQTB, ta hy tm hiu v cu trc v
tnh cht chung ca -Al2O3.
I.2.1. Cu trc ca -Al2O3:
Cu trc ca nhm oxit c xy dng t cc n lp ca cc qu cu b
xp cht, lp ny c dng tm i m mi ion O 2- c nh v v tr 1. Lp
tip theo c phn b trn lp th nht, tt c cc qu cu th hai nm v
tr lm su ca lp th nht (v tr 2). Lp th ba c phn b trn cc h su
khc ca lp th nht (v tr 3)

1
2
1
2
1
2
1

1
3
1
2

2
1
3
1

Hnh 3: Cu trc khi ca - Al2O3.

Cc cation kim loi trong Al3+ nht thit c phn b trong khng gian
gia cc lp b cht anion. L hng duy nht m ion Al 3+ c th phn b l gia
hai lp. Mt kh nng khc, cc ion Al 3+ nm v tr trn l hng tam gic, lp
oxy th hai thuc v tr 2 c phn b trn ion Al 3+. Ion Al3+ trong trng hp ny
nm v tr tm bt din

Al3+

Hnh 4: S phn b ca Al3+ trong mng khng gian.

Lp oxy th hai ca oxit trong v tr 2 phn b trn Al3+. Nu tip tc sp
xp bng phng php ny th mt ion Al3+ c bao bc bi 3 ion oxy, tho
mn trung ho in tch th cn thit phi trng mt trong ba v tr ca cation.
S thiu vng ny dn n kh nng sp xp trong mng thnh cc hnh lc gic
u m nh l cc Al3+

1
1

O21
Al3+

1
1

1
1

1
1

Hnh 5: V tr ion Al3+ trong cu trc b cht anion.

Khi tch nc cu trc c th a n cu trc b cht khi lc din chuyn

sang lp phng. Trong cu trc lp phng b cht khi bt din rng cha cc
ion nm trung tm, ng thi khi bt din kt hp vi khi t din v to
khong khng gian cho cc cation b. Al3+ c th vo khi bt din v t din.

Hnh 6: Hai lp u tin ca tinh th - Al2O3

Trong nhm oxit oxy c bao gi theo kiu khi lp phng b cht, cn
i vi cation th mt trong hai cation nm khi 4 mt, cation kia nm trong khi
8 mt. trng hp ny khi c mt hydro th cng thc ca -Al2O3 v - Al2O3
c th vit tng ng: (H1/2Al1/2)Al2O4 hay Al(H1/2Al3/4)O4 trong cc ion nhm
nm trong khi t din. Proton khng nm trong l trng t din m nm trn b
mt trong dng nhm OH-. Nh vy mt trong 8 ion O 2- nm trn b mt trong
dng OH-. iu c ngha tinh th b v phn ln cc nhm OH - nm trn b
mt. V vy - Al2O3 v - Al2O3 c din tch b mt ln v trn b mt cha nhiu
OH- lin kt.
Cc nhm oxit khc nhau v t l ion nhm trong khi t din v bt din,
cng nh mc bao bc i xng ion Al 3+ trong l trng t v bt din. - Al2O3
cha ion Al3+ trong khi t din ln hn trong - Al2O3.
- Al2O3 c cu trc lp phng b cht, c 2 dng phn b ion Al 3+. Dng
th 1 to thnh do s chuyn dch 2/3 cation t v tr bt din sang t din. Dng

10

th 2, ion Al3+ ch phn b trong l trng bt din. Trong - Al2O3, lp th 2 ion

Al3+ ch phn b trong l trng bt din, cn lp th nht ion Al 3+ phn b u
trong l trng t v bt din.
I.2.2. Tnh cht b mt ca -Al2O3:
Tnh cht ha hc b mt ca -Al2O3 lin quan trc tip n tnh cht xc
tc v hp ph ca chng. -Al2O3 hot tnh, ngoi Al2O3 tinh khit thng cha t
1 5% nc. Ph thuc vo iu kin ch to, trong -Al2O3 c th cha oxit kim
loi kim, oxit st, ion sunfat. Cc tp cht ny c nh hng n tnh cht xc tc
ca -Al2O3. V d nh s c mt ca SO 42- v mt s anion khc lm tng axit
ca -Al2O3 .
Ph thuc vo nhit , -Al2O3 c th hp ph nc dng phn t H 2O
hoc dng ion OH-. Khi tip xc vi hi nc nhit thng, -Al2O3 hp ph
nc dng phn t H2O khng phn ly. Nc lin kt vi b mt bng lin kt
hidro bn vng. p sut hi nc cao, quan st thy qu trnh hp ph vt l mt
lng nc ln, nhng lng nc ny d tch ra khi nung mu nhit 120 0C.
Bng phng php ph hng ngoi chng minh c rng, nhit thp trn
b mt -Al2O3 tn ti nc dng khng phn ly, khi sy mu 3000C lng
nc phn t khng b tch khi b mt to nn nhm hidroxyl b mt .
nhit cao, ion OH - dn tch khi oxit dng H 2O, nhng ngay c
nhit 800 10000C v p sut chn khng trong nhm oxit vn cha mt lng
nc nht nh.
Ion OH- th hin tnh cht tm axit Bronsted. Trong qu trnh dehidrat ha,
hai nhm OH- hp li to thnh mt phn t nc, ion oxi li trn b mt to nn
cu oxi. mt kha cnh khc c th thy rng khi hai nhm OH - cnh nhau tc
dng li mt nguyn t nhm thiu in t v n th hin nh mt tm Lewis.
Nh vy, trn b mt nhm oxit tn ti c hai loi tm: tm Bronsted v Lewis.
Tm Bronsted v Lewis l cc trung tm xc tc hot tnh trn b mt nhm oxit

11

I.2.3. Cu trc xp ca -Al2O3:

A. Din tch b mt ring:
-Al2O3 i t gel Bemite c din tch b mt vo khong 150 250m2/g,
cha nhiu l xp c ng knh t 30120A0 v th tch l xp t 0,51 cm3/g .
Din tch b mt ring ca oxit nhm ph thuc vo c nhit nung, thi gian
nung, bu khng kh tin hnh nung. Do mun thu c oxit nhm c din tch
b mt ring cao ta phi la chn ch nung thch hp. Thc nghim cho thy
tt nht l nn nung tng lp mng, c dng khng kh i qua.
B. Kch thc v th tch l xp -Al2O3:
Hu ht din tch b mt ca oxit nhm i t Gibbsite, Bayerit hoc Bemit
u c ngun gc t nhng l xp rt nh khong 1020 A0 . Nhng l xp ny
bt ngun t nhng khe h ca mt phin tinh th hoc khong trng gia cc
phin tinh th oxit nhm ring bit.
Mc d c nhiu l xp c kch thc ln nhng trong oxit nhm c
ngun gc t trihidroxit nhm th nhng l xp nh vn quyt nh phn ln trong
b mt v chim tng th tch l xp.
c tnh cu trc ca oxit nhm cng thay i theo nhit nung. Khi
nung qu nhit m ti oxit nhm thu c c din tch b mt ln nht, oxit
nhm bt u b sp cu trc (thiu kt) dn n gim din tch b mt v th tch
l xp. Tng th tch l xp ln nht ca oxit nhm thu c t trihidroxit nhm
l 0,5 cm3/g .
C. Tnh axit ca -Al2O3:
Ph thuc vo mc dehidrat ha, trn b mt -Al2O3 c th tn ti hai
loi tm axit: tm axit Bronsted v tm axit Lewis. Tm axit Bronsted hnh thnh
do s tn ti ca cc nhm OH - khi vn cn mt lng nc cha b tch ra ht
khi oxit nhm. Tm Lewis hnh thnh trong qu trnh dehidrat ha. l khi hai

12

nhm OH- cnh nhau tc dng li mt nguyn t nhm thiu in t v n th

hin nh mt tm Lewis.
Nhn chung, nhm oxit hidrat ha khng biu hin tnh axit mnh. Nhm
OH- lin kt vi ion nhm trong t din c kh nng biu th tnh axit ln hn.
axit ca nhm OH- trn b mt tng mnh khi cnh c ion Cl -. iu ny c
gii thch do s chuyn dch in t t nhm OH- sang nhm Cl-.
Khi chuyn mt phn b mt nhm oxit c hidrat ha hon ton:
OH-

OHAl3+

OH-

OH-

Al3+

OHAl3+

OHAl3+

sang b mt c cha Cl- v OH- (v d nh hot ha b mt bng HCl)

Cl-

OHAl3+

Cl-

OH-

Al3+

ClAl3+

OHAl3+

lm tng mnh tnh axit ca cc nhm OH - cn li. Tnh axit ca nhm oxit tng
dn khi tng s Cl- thay th OH- trn b mt nhm oxit. Nh vy, trn b mt
nhm oxit c th thay i axit cng nh s tm axit. Hiu ng ny tng mnh
hn khi proton d dng thay th bng cch ni qua oxi vi nhm trong t din
Cc tm axit Bronsted v Lewis c xem l cc tm hot tnh c vai tr
ln trong nhiu phn ng xc tc. -Al2O3 ng vai tr xc tc cho phn ng
isome ha, v d nh chuyn dch ni i trong buten. Trong khi , do tnh axit
yu nn chng hu nh khng c hot tnh trong ng phn ha mch. tng
hot tnh xc tc ca nhm oxit trong cc phn ng ng phn ha mch
hydrocacbon, cracking, reforming cn tng tnh axit ca nhm oxit bng cch
hot ha HCl hoc HF.
I.3. VT LIU MESOPOROUS V MESOPOROUS -Al2O3
I.3.1. Gii thiu chung v vt liu MQTB

13

 -Al2O3 l mt loi vt liu mao qun. Theo qui nh ca hip hi IUPAC

(International Union of Pure and Applied Chemistry) th vt liu mao qun c th
chia lm 3 loi :
Vt liu vi mao qun: ng knh l xp d < 2nm.
V d: zeolit v cc vt liu c cu trc tng t zeolit nh aluminosilicat,
aluminophotphat...
Vt liu mao qun trung bnh: ng knh l xp 2nm < d < 50nm.
V d: M41S, MSU, SBA, ...
Vt liu mao qun ln: ng knh l xp d > 50nm.
V d: cc gel mao qun, thu tinh mao qun...
Trong ba loi vt liu k trn, th vt liu MQTB hay cn gi l vt liu
mesopore l hay gp nht v c tc dng rt ln trong nghin cu xc tc d th.
Vt liu mesopore l mt trong nhng vt liu quan trng trong ha hc hp ph
v xc tc v n c tnh cht chn lc cao. Cc loi vt liu oxit nh oxit silic, oxit
nhm, oxit titan v oxit zircon vi kch thc l xp trung bnh c nhiu c tnh
tt, c th ng dng lm cht mang v cht hp ph chn lc trong cng nghip
lc ha du.
Vt liu mesopore l vt liu c cu trc l nhng l mao qun trung bnh,
c h thng mao qun sp xp ng nht vi kch thc l xp t 20-200 nn n
cho php cc phn t c kch thc ln khuych tn v chuyn ha qua mao qun.
Vt liu MQTB khc phc c nhng hn ch ca cc loi zeolite vi ng
knh mao qun c 10. Tuy hot tnh xc tc khng cao bng zeolite nhng
chn lc ca n cao hn.
Vic tm ra phng php tng hp h vt liu MQTB u thp k 90 m
ra hng nghin cu mi trong lnh vc nghin cu xc tc. H vt liu ny c
k hiu l M41S c cu trc mao qun vi trt t rt cao v kch thc mao
qun rt ng u. Kch thc mao qun c th dao ng trong khong rng t
20-100, tu thuc vo iu kin tng hp nh: bn cht cht hot ng b mt,

14

bn cht tin cht v c, nhit phn ng... H vt liu ny gm nhiu dng:

MCM-41 (cu trc lc lng), MCM-48 (cu trc lp phng), MCM-50 (cu trc
lp mng).
Nhng nm gn y, cc nh khoa hc tng hp c h vt liu MQTB
mi k hiu SBA. Vt liu ny c trt t cao, kch thc mao qun c th ln
ti 500. Cu trc ca SBA ph thuc ch yu vo loi cht hot ng b mt
c s dng v cho n nay h SBA c 16 loi t SBA-1 n SBA-16.
I.3.2 Phn loi vt liu MQTB
Ngi ta c th phn loi vt liu MQTB theo cu trc ca chng theo cc
dng sau
Cu trc lc lng (hexagonal) : MCM-41, SBA-15.
Cu trc lp phng (cubic)

: MCM-48, SBA-16.

Cu trc lp mng (laminar) : MCM-50.

a - Lc lng

b - Lp phng

c - Lp mng

Hnh7: Cc dng cu trc ca vt liu MQTB

Da vo thnh phn vt liu th chia vt liu MQTB thnh 2 nhm:
Vt liu MQTB cha silic : MCM, SBA. Trong nhm ny cn bao
gm cc vt liu MQTB c th thay th mt phn silic mng li
bng cc kim loi khc nh Ti, Al, Ru
Vt liu MQTB khng cha silic: ZrO2, TiO2
I.3.3. Cc dng ng ng nhit hp ph v nh hp ph ca vt liu
MQTB
15

Cc loi vt liu mao qun khc nhau cho dng ng ng nhit hp ph

v nh hp ph cng khc nhau. ng ng nhit hp ph v nh hp ph ca vt
liu MQTB khng trng nhau, to ra vng tr. Hnh dng vng tr cho ta nhng
thng tin v hnh dng mao qun. C rt nhiu loi mao qun v cng c rt nhiu
vng tr khc nhau. De Boer ngh ra 5 dng vng tr khc nhau, nhng cch
phn chia qu phc tp. n gin ta chia vt liu MQTB thnh 3 loi da theo
ng ng nhit hp ph v nh hp ph.
Trng hp mao qun hnh tr hoc hnh khe, ta c ng ng nhit hp
ph v nh hp ph trn hnh 8a v hnh dng mao qun trn hnh 9a.
Trng hp mao qun hp pha di cho ta ng ng nhit hp ph v
nh hp ph trn hnh 8b v hnh dng mao qun trn hnh 9b.
Trng hp mao qun hnh l mc trn nh di to hay gi l hnh c chai
th hin ng ng nhit hp ph v nh hp ph trn hnh 8c v hnh dng mao
qun trn hnh 9c.

a)

b)

c)

Hnh 8: Ba dng ng ng nhit hp ph v nh hp ph ca vt liu MQTB

16

a)

b)

c)

Hnh 9: Ba dng mao qun ph bin ca vt liu MQTB

I.3.4. Thnh phn tng hp vt liu MQTB
tng hp c vt liu MQTB cn t nht 3 thnh phn sau:
A. Ngun cht v c:
Cha thnh phn chnh l Silic, nhm. y l thnh phn quan trng trong
vic to mng li vt liu mao qun trung bnh.
Ngun cht v c cha Si v Al nh t st. T nhng ngun cht v c ny
ngi ta iu ch ra vt liu mao qun trung bnh c cha Si hay vt liu thay th
mt phn Si trong mng li nh vanadosilicat, zirconosilicat, borosilicat,
titanosilicat, gallosilicat tng thm tnh nng ng dng ca cc vt liu ny.
B. Cht nh hng to cu trc:
Cht to cu trc thng l cc cht hot ng b mt cha mt u a
nc v mt ui mch di k nc nh : Xetyl trimetyl amoni bromua C12H25N(CH3)3Br, axit tactaric, axit citric,axit lactic, polyme ... Nng ca cht
hot ng b mt trong dung dch l tham s quan trng cho s hnh thnh mixen,
hnh dng mixen v s sp xp ca mixen thnh pha tinh th lng.
Chnh cht hot ng b mt s hnh thnh nn cu trc ca vt liu. S t
tp cht hot ng b mt to mixen dng que, dng lp mng hay cu trc 3D.

17

Hnh 10: nh hng ca nng cht HBM ti s hnh thnh cu trc

Ti nng thp cc phn t cht hot ng b mt tn ti dng monome
ring bit. Khi tng nng n mt gi tr nht nh, cc phn t cht hot ng
b mt bt u t sp xp thnh cc mixen hnh cu. Nng ti cc mixen bt
u hnh thnh gi l nng mixen ti hn. Khi nng tip tc tng s to
thnh cc mixen hnh tr v cui cng l cc pha tinh th lng dng lc lng, lp
phng hoc dng lp . Trong mt s trng hp khc c th hnh thnh pha tinh
th lng dng lp phng trc khi hnh thnh pha tinh th lng dng lp.
C. Dung mi:
Dung mi l thnh phn khng th thiu trong tng hp vt liu mao qun
trung bnh. Dung mi c tc dng ho tan cht hot ng b mt, hay to vi cht
hot ng b mt hn hp nh tng d dng to lin kt gia tin cht v c
v mixen.
c rt nhiu dung mi c s dng da trn c tnh ca dung mi
l: dung mi phn cc d ho tan nhng hp cht phn cc v ngc li, dung mi
khng phn cc d ho tan nhng hp cht khng phn cc.
Trong sn xut cng nghip cn quan tm ti gi thnh, phn cc, d
kim, t c hi... s dng cho hp l v ti u nht nh th s to ra cc sn
phm mong mun v c gi thnh va phi.
Cc loi dung mi thng c s dng trong qu trnh tng hp vt liu

18

mao qun trung bnh l: nc, etanol, 1,3,5-trimetylbenzen,......

I.3.5. C ch hnh thnh cu trc vt liu MQTB
Hin nay c rt nhiu c ch c a ra gii thch qu trnh hnh thnh
cc vt liu MQTB. Cc c ch u khng nh mt c im chung l s tng
tc ca cc cht HBM vi cc tin cht v c trong dung dch .
Cht hot ng b mt + Tin cht v c = Vt liu MQTB

Hnh11: C ch tng hp vt liu MQTB

Do c nhiu loi tng tc khc nhau gia cc tin cht v c vi cc cht
HBM dn n cc c ch tng hp khc nhau, phng php tng hp khc nhau
v kt qu l to ra cc hp cht MQTB c hnh dng v kch thc mao qun
khc nhau. C mt s c ch nh :
A. C ch nh hng theo tinh th lng (Liquid Crystal Templating)
C ch nh hng theo tinh th lng c cc nh nghin cu ca hng
Mobil-Oil a ra gii thch cho s hnh thnh ca h vt liu mao qun trung
bnh M41S. Cu trc vt liu MQTB ph thuc vo di ca mch cacbon cng
nh nhm chc ca cht HBM, ph thuc vo nng ca cht HBM. Theo
c ch ny trong dung dch cc cht HBM t sp xp thnh pha tinh th lng c
19

dng mixen ng, thnh ng l cc u a nc ca cc phn t cht HBM v

ui mch hydrocacbon di k nc hng vo pha trong. Nhng mixen ng ny
ng vai tr cht to cu trc v sp xp thnh cu trc tinh th dng lc lng

Hnh12: C ch nh hng theo cu trc tinh th lng

Sau khi thm ngun silic vo dung dch, cc phn t cha silic tng tc vi
cc u phn cc ca cht HBM thng qua cc tng tc tnh in (S+I-, S-I+,
trong S l cht HBM, I l tin cht v c) hoc tng tc hydro (S0I0) v hnh
thnh nn lp mng silicat xung quanh mixen ng. Qu trnh polymer ho ngng
t silicat to nn tng v nh hnh ca vt liu oxyt silic MQTB. C ch ny
c th hin theo ng (1). Nhng trong nhng nghin cu v c ch hnh
thnh bng cc phng php hin i th ngi ta a ra c ch hnh thnh cu
trc tinh th lng l theo ng (2), v nng cht hot ng b mt thp hn
nhiu so vi nng mixen ti hn. Nh vy, cc mixen ng khng t sp xp
thnh cu trc tinh th lng m cu trc ny ch hnh thnh sau khi thm tin cht
v c, trong nghin cu ny ngun cht v c l silicat, v cc silicat ng hnh
thnh sau khi thm ngun silicat s t sp xp thnh cu trc lc lng.
B. C ch sp xp silicat ng (Silicate Rod Assembly)
Bng vic nghin cu ph cng hng t ht nhn

14

N, David thy rng

khng xut hin pha tinh th lng trong qu trnh tng hp vt liu MQTB MCM41. Do vy ngi ta gi thit rng ban u 2 hoc 3 lp mng silicat ph ln trn
mi mixen ng cht hot ng b mt ring bit, cc ng ny bt u sp xp hn
20

lon, sau mi sp xp thnh cu trc lc lng, thc hin qu trnh gia nhit v
lm gi ngng t silicat s to thnh hp cht MQTB MCM-41 (hnh 13).

Hnh 13: C ch sp xp silicat ng

C. C ch to lp silicat trung gian (Silicate Layer Intermediate)
Silicat tp hp thnh cc lp v gia b mt tip xc ca cc ng hnh tr
c tng tc. C ch gm cc giai on sau: hn hp ban u c cu trc lp
mng c hnh thnh t lc tnh in gia cc anion silicat v cation cht hot
ng b mt. Khi cc phn t silicat ngng t, lm mt in tch ca chng
gim. Cng vi qu trnh ny, cc lp silicat b un cong cn bng mt in
tch vi nhm chc ca cht hot ng b mt. Do cu trc MQTB lp mng
chuyn ho thnh cu trc mao qun trung bnh lc lng .

.
Hnh 14: C ch to lp silicat trung gian

21

D. C ch silicate gp (Silicate Layer Puckering)

Thay bng s to thnh ca cc que mixen c bao bc bi cht v c,
Steel et al a ra nhn nh rng nhng que mixen hnh tr sp xp vo gia
nhng lp cht v c. Khi gi ha hn hp, cc lp v c s dm d li v ph v
mixen, sau chuyn thnh cu trc MQTB cha cht hot ng b mt .

Hnh 15: Hnh minh ha s co li ca cc lp cht v c

E. C ch phi hp to cu trc (Cooperative Templating)
Steel nhn thy iu kin nhit thp v pH cao (xp x 14) v khi c
mt silicat th cc phn t cht hot ng v silicat ng tp hp to ra tinh th
lng dng lc lng. Sy v nung pha trn s to ra vt liu MQTB

Hnh 16: C ch phi hp to cu trc

22

Cc c ch ny u da trn s tng tc ca cht HBM vi ngun cht

v c. Ty theo cht HBM m c s tng tc khc nhau do c tnh, cu
trc khc nhau c hnh thnh.
I.3.6. Cht nh hng to cu trc
nh hng to cu trc l qu trnh cc oxit t chc thnh mng li tinh
th xung quanh cc cu trc trung tm to ra bi cc cht hu c. Trong trng
hp n gin nht l vt liu mao qun c cu trc tng t nh dng hnh hc
ca phn t hu c. Trng hp khc l cc phn t hu c t hp thnh cc cu
trc khc nhau (cc phn t hu c ny l cc cht HBM c phn t lng ln
hnh thnh nn vt liu MQTB). Hai trng hp ny c minh ha hnh 17

Hnh17 : S hnh thnh nn mng li vi mao qun s dng tc nhn to cu

trc amin bc bn c chui alkyl ngn (a) v s hnh thnh mng li vt liu
MQTB s dng cht to cu trc c chui alkyl di (b)
Mt trong nhng i hi quan trng nht trong vic tng hp cc vt liu
MQTB l vic s dng cc cht HBM lm cht nh hng to cu trc to ra
nhng l xp c cu trc v kch thc mong mun. Nhng nghin cu gn y
nht tp trung vo vic tm ra nhng cht to cu trc mi hoc s dng hn hp
mt s cht to cu trc, thng cc polyme to ra nhng l xp dng

23

hexagonal (lc lng) v cubic (lp phng) hoc nhng l xp khng gian c trt
t v lp li.
A. Vai tr ca cht nh hng to cu trc
Cht nh hng to cu trc gi cc vai tr sau:
T chc mng li thng qua vic lp y cc l xp, lm cn bng
in tch.
To nn hnh thi cu trc cho cc knh mao qun thng qua hnh dng,
kch thc ca chng.
Lm gim th ho hc ca mng li hnh thnh nh to nn cc tng
tc vi cc cht v c (lin kt hydro lin phn t, tng tc tnh in...
B. iu kin i vi cht nh hng to cu trc
Cht nh hng to cu trc trong vt liu MQTB l cc cht HBM c
mt u phn cc a nc v mt ui di k nc. N cn phi tha mn cc
iu kin sau :
C kh nng ha tan tt trong dung dch
Bn di cc iu kin tng hp
C kh nng lm bn mng li mao qun c hnh thnh
Tch khi vt liu m khng ph hy khung.
C. Phn loi cht nh hng to cu trc
Cht nh hng to cu trc rt a dng v c phn loi theo phn tch
in ca chng. Thng c chia lm ba loi sau:
Loi cation: Thng l cc mui amin nh xetyl trimetyl amoni bromua
C16H33(CH3)3NBr.
Loi anion: Cc hp cht hu c cha nhm SO3 Loi khng ion: cc ankylpoly (etylen oxyt), nh C 16H33(CH2CH2O)20,
hay cc copolyme cha cc chui polyetylen oxyt v polypropylen oxyt.

24

Hnh 18: Mt s dng hnh hc chnh ca cc mixen cht HBM: Hnh cu

(MIC), hnh tr (CYL), lp (LAM), dng lp un (MLAM), dng lp c cc l hnh
tr (HPL), 3D (Ia3d), cc hnh tr sp xp c trt t (HEX), lp phng (BBC)
D. Cc phng php loi cht to cu trc
to ra h thng mao qun th cn loi b cht to cu trc chim y
khong trng bn trong. C rt nhiu phng php loi b cht to cu trc nh:
Nung vt liu;
Chit dung mi;
Dng l vi sng;
Sau khi hnh thnh cu trc, cc cht HBM s c loi b nh phn
ng phn hu nhit l ch yu (nung nhit cao). V d qu trnh loi cht tao
cu trc trong SBA-15
I.4. ng dng ca nhm oxit
I.4.1. ng dng ca Al2O3 ni chung.
Cc ng dng quan trng ca xit nhm l lm cht hp ph, cht xc tc
hoc cht mang xc tc. Trong , ng dng quan trng nht l lm cht mang xc
25

tc. Tu lnh vc s dng v dng Al 2O3 c s dng m n l cht mang xc tc

tr, c tng tc vi nn hay cht mang a chc nng.
Khi c s dng lm cht mang tr, ngi ta thng dng ch yu l dng
alpha v n c tnh tr ho hc, bn c hc nn c th chu ng c nhng
iu kin mi trng khc nghit. Mt khc, do c tnh cht tr v mt ho hc
nn n khng gy ra cc phn ng ph khng mong mun, khng lm mt hot
tnh ha hc v tnh cht chn lc ca xc tc v c bit l khng c kh nng
gy ng c xc tc.
i vi cht mang c tng tc vi nn, cc yu t v cc qu trnh x l
c ngha ht sc quan trng trong vic phn b, hot ho v to bn cho xc
tc.
i vi cht mang a chc nng, ngoi chc nng thng thng nh: phn
tn pha hot ng ca xc tc, tng din tch tip xc ca pha hot ng xc tc
vi mi trng, ngn cn qu trnh thiu kt v ti kt tinh pha hot ng, tng
bn, tng kh nng truyn nhit ca xc tcn cn c vai tr h tr xc tc
ging nh mt xc tc th 2. Trong lnh vc ny, gamma nhm oxit thng c
s dng.
Mt s ng dng quan trng ca oxit nhm trong cng nghip c tm tt
trong bng 1:
Bng 1: Mt s ng dng ca oxit nhm.
Cc ng dng

Vai tr ca Al2O3

V d sn xut

Ankyl ho

Xc tc

Phenol

Dehyr ho

Xc tc

Axit focmic

Xc tc

1- metylxyclohexan

Cht mang

Isophtaonitril

Hydr desunfua ho

Cht mang

Tinh ch du

Hyr denit ho

Cht mang

Tinh ch du

Isome ho

26

Reforminh v vng ho

Cracking

Hyr ho

Polyme ho
Oxi ho tng phn

Xc tc

Phenolhydrozon

v Cht mang

Cyclohexan

Xc tc

Hyrcacbon

v Cht mang

Naphtalen

Xc tc

Etyl ete

v Cht mang

Ancol khng no

Xc tc

Xyclolefin

v Cht mang

Etylenoxit

Cht mang

Etylenoxit

I.4.2. ng dng ca - Al2O3.

Do c cc c tnh l b mt ring ln, cu trc xp, hot tnh cao, bn c,
bn nhit nn - Al2O3 c s dng rng ri trong cc lnh vc nh lc ha du,
xc tc cho cc phn ng ha hc, cht hp ph
a. ng dng trong lc ha du:
Trong cng ngh lc ha du - Al2O3 c dng lm xc tc tch cc
cu t khng mong mun, bo v thit b lc du, tng cht lng sn phm. Qu
trnh Clause, - Al2O3 c s dng nhm chuyn ha H2S thnh mui sunfua.
Trong qu trnh x l bng hydro, - Al2O3 c s dng nh mt cht mang xc
tc tch cc hp cht hu c c cha lu hunh, nit
Trong qu trnh isome ha, - Al2O3 lm cht mang phn tn Pt to xc
tc Pt/- Al2O3 cho phn ng. Ngy nay Pt/- Al2O3 cng c s dng lm xc tc
lng chc trong qu trnh reforming, trong Pt mang chc nng oxy ha kh,
xc tin cho phn ng hydro ha, dehydro ha cn Al2O3 l cht mang c tnh axit,
ng vai tr chc nng axit baz thc y phn ng izome ha, hydrocracking.

27

b. ng dng lm cht hp ph:

Do c th tch mao qun v din tch b mt ln, mt trong nhng ng
dng chnh ca - Al2O3 MQTB l lm cht hp ph. Nhm oxit c vai tr quan
trng trong vic lm kh cht lng v kh, hp ph chn lc trong ngnh xng du
Nhm oxit MQTB c th hp ph hi nc trong qu trnh bo qun mc
m ca khng kh trong cc thit b, my mc c bit v kho cha, lm kh
cc vt liu nhit thp, bo v cc tranzito v cc phn t bn dn.
- Al2O3 MQTB c th hp ph hn hp ca cc hydrocacbon nh (C 1
C3), hoc cc kh c nhit si thp. lm giu v tinh ch cc phn on du
nh phn tch cc hp cht vng t cc parafin hay olefin th nhm oxit c th hp
ph hn hp cc vng thm, vng no. Nhm oxit cng c th hp ph hn hp ca
cc hydrocacbon cha bo ha c nhit si cao, cc hp cht mu t sp, du,
cht bo
Nhm oxit MQTB hp ph hn hp kh c nhit si thp nh: cc kh
him, khng kh, nit oxit, metan, axetylen trong qu trnh phn tch.
Trn thc t Mitsubishi Heavy Industries s dng nhm oxit MQTB cho
qu trnh thu hi cc hp cht hu c d bay hi (VOC). Do c din tch b mt
ln m ngi ta c th thc hin qu trnh hp ph VOC ngay nhit thng.
S hp ph bo ha xy ra vi dng khng kh nng 120 1500C
I.4.3. Trin vng pht trin sn xut -Al2O3
Kt qu thm d a cht pht hin trn lnh th nc ta c tr lng
qung boxit phong ph c Min Bc v Min Nam Vit Nam. Tng tr lng
qung boxit ca Vit Nam c tnh khong 8 t tn, trong c 7,6 t tn cc
tnh Ty Nguyn. Vi tr lng nh vy, nc ta ng trong s cc nc c tr
lng bxit ln trn th gii
Nc ta nm trong khu vc c nhu cu nhp khu nhm vo loi ln nht
trn th gii. Hng nm cc nc ASEAN, Nht Bn, Hn Quc, i Loan phi

28

nhp trn 4 triu tn nhm, Trung Quc v Nga nhp 3-4 triu tn alumin in
phn nhm. Vi v tr a l thun li v mi quan h kinh t truyn thng, y l
th trng khu vc tim tng cho cc sn phm nhm ca nc ta.
Tuy l nc c tr lng qung nhm kh ln nhng nu ch xut khu
qung hoc cc sn phm n gin th gi tr kinh t t c khng cao. Do
cn phi nghin cu xy dng cc nh my ch bin sn xut cc vt liu nhm
c bit l -Al2O3. Di y l mt s dn chng thy r gi tr kinh t khi
nghin cu v pht trin sn xut -Al2O3:
Nh my lc du s 1 Dung Qut cng phi nhp nhm oxit hot tnh v
xc tc cha nhm (np my ln u cn ~ 100T -Al2O3). Trong thi gian ti
nc ta s xy dng thm mt s nh my lc du v nh vy nhu cu v xc tc
-Al2O3 ngy cng tng ln.
Hin nay ti Khnh Ho ang s dng -Al2O3 X l nc b nhim flo
cho nhn dn Ninh Ho. -Al2O3 phi nhp hon ton t nc ngoi.
Hin nay cc cng trnh nghin cu v sn xut xc tc -Al2O3 ang c
quan tm ng k. Chng ta hon ton c th hin thc ha cc cng trnh nghin
cu p dng vo thc t.
Da trn ngun ti nguyn qung nhm di do chng ta c th dng mt
phn sn xut -Al2O3 vi gi tr kinh t cao
Nghin cu v -Al2O3 khng ngng c m rng chnh v th trin vng
pht trin sn xut -Al2O3 nc ta l rt ln.

29

CHNG II : THC NGHIM

II.1. DNG C V HO CHT TH NGHIM
Trong n ny, em tin hnh iu ch hydroxit nhm v nhm oxit t
nhm ph liu, cc ho cht v dng c cn thit nh sau:
II.1.1. Ho cht th nghim :
+ Phn nhm cng nghip
+ Dung dch kim NaOH 25%.
+ Cht oxi ha (H2O2)

+ Cc cht hot ng b mt lm tc nhn cu trc

+ Dung mi l: nc ct, etanol.
+ Nhm Al(NO3)3
+ BaCl2.
+ Giy lc.
+ Giy th pH
II.1.2. Dng c th nghim:

30

+ Cc phn ng cc loi 1000ml, 500ml, 200ml, 40ml.

+ Phu lc Bucher, bnh lc
+ Thit b lc chn khng.
+ Thit b khuy.
+ T sy, t nung
+ Cn phn tch, cn khi lng ln
+ Chn,a nung.

II.2. QUY TRNH THC NGHIM

Bc 1: To dung dch Natri aluminat:
Nguyn liu

H2O2
Lng,
Lc

Nguyn liu sch

NaOH 25%

D.D Aluminat
H2O2

Lng, lc

D.D Aluminat sch

Phn nhm c cn theo s liu tnh ton ri ho tan vo mt nc. Qua
qu trnh lc tch thu c nguyn liu sch, sau cho t t dung dch phn vo
dung dch NaOH n khi kt ta trng c tan ht thnh dung dch NaAlO 2. Cho
dung dch hydro peroxit (H2O2) vo dung dch NaAlO2 khuy u H2O2 oxy ha
cc hp cht hu c v cc ion Fe 2+ thnh cc ion Fe3+ trong dung dch. Sau
dung dch c lng khong 24 gi cc cht khng tan dng keo hoc ht
lng ht. Phn dung dch trn c tch ra v lc bng phu Buchner ta thu c
dung dch aluminat natri trong.

31

 giai on ny pH > 12 ton b cc ion nh Cu 2+, Fe3+, Cr3+, Pb2+, Zn2+,

Co2+, Mn2+, Ni2+, Mg2+ c th to kt ta dng hydroxit, lng xung v b loi khi
dung dch v trong cc ion trn th tch s tan ca Fe(OH) 3 l b nht ( TFe(OH)3 =
4.10-38), tch s tan ca Mg(OH)2 l ln nht ( TMg(OH)2 = 4.10-12) nn pH = 12
th ion Mg2+ c th b loi ti a v nh vy cc ion cn li c tch s tan nh hn
cng s b loi.

Bc 2: iu ch nhm oxit

DD Aluminat
Al(NO3)3

80oC 24h
Beomite

Beomite
Gi ha

Cht to cu
trc

Sy 110oC
Beomite kh
180oC(3h)230oC(3h)500oC(5h)

Nung
-Al2O3

Nhm nitrat c ha tan trong nuc, ha tan cht to cu trc trong dung
mi v cho vo dung dch Nhm nitorat , khuy t ng u, sau cho
32

phn ng vi dung dch aluminat to boehmit. Sn phm thu c gi ha

80oC trong vng 24h. Sau , em lc ly sn phm, qu trnh lc, ra sn phm
nhiu ln v th kim tra nng gc sulfat bng BaCl 2. Sn phm rn thu c
t qu trnh lc ra em sy 110oC trong vng 5h, tip tc nung 180oC trong
vng 3h, 230oC trong 3h, 500oC trong 5h thu c sn phm l -Al2O3.
II.3. CC PHNG PHP NGHIN CU C TRNG CA VT LIU
C nhiu phng php nghin cu c trng ca MQTB oxit nhm nh:
phng php nhiu x tia X nghin cu nh tnh pha tinh th, phng php
hin vi in t nghin cu b mt kch thc hnh dng vi tinh th, phng
php gii hp ph NH3 theo chng trnh nhit tnh tm axit, phng php
BET xc nh b mt ring v phn b l xp ca cht mang v xc tc, phng
php phn tch nhit. Trong phm vi n ny ta ch p dng cc phng php
sau.
II.3.1. Nghin cu nh tnh pha tinh th bng nhiu x Rnghen
Phng php nhiu x tia X hay cn gi l phng php nhiu x Rnghen
l mt phng php hin i, c ng dng mt cch ph bin nghin cu vt
liu c cu trc tinh th.
Nguyn tc:
Theo l thuyt cu to tinh th, mng tinh th c xy dng t cc nguyn
t hay ion phn b u n trong khng gian theo mt qui lut nht nh. Khi
chm tia Rnghen hay cn gi l tia X ti b mt tinh th v i su vo bn trong
mng li tinh th th mng li ny ng vai tr nh mt cch t nhiu x c
bit. Cc nguyn t, ion b kch thch bi chm tia X s thnh cc tm pht ra cc
tia phn x. M cc nguyn t, ion ny c phn b trn cc mt song song nn
hiu quang trnh ca 2 tia phn x bt k trn hai mt phng song song cnh nhau
c tnh nh sau:
= 2d. sin.
Trong :

d: l khong cch gia 2 mt phng song song

33

: l gc gia chm tia X v mt phng phn x.

Theo iu kin giao thoa, cc sng phn x trn 2 mt phng cng pha th
hiu quang trnh s bng nguyn ln di sng. Nn ta c :
2d. sin = n

( h thc Vufl - Bragg ).

y l phng trnh c bn nghin cu cu trc mng tinh th. Cn c

vo cu trc cc i nhiu x trn gin , tm c 2 . T suy ra d theo h
thc Vufl - Bragg. So snh gi tr d tm c vi d chun s xc nh c thnh
phn cu trc mng tinh th ca cht cn nghin cu. y l phng php c s
dng rng ri trong nghin cu cu trc tinh th ca vt cht.
Vt liu mao qun trung bnh l vt liu gi tinh th c cu trc mao qun
rt trt t nhng thnh mao qun dng v nh hnh. Xt theo trt t xa th vt
liu mao qun trung bnh c h thng mao qun vi trt t cao, phn b c qui
lut theo khong cch cng nh b tr trong khng gian tng t ca tinh th. Do
chng s c cc pic c trng trn ph nhiu x tia X, da vo cc pic ny c
th xc nh c cu trc ca vt liu l lc lng, lp phng hay lp mng. V
da vo ph nhiu x tia X cn c th xc nh c tinh khit ca vt liu.
Thc nghim:
Gin XRD c ghi trn my D5005-Brucker-c, s dng ng pht tia
X bng Cu vi bc sng K = 1,54056A0 , in p 40KV, cng dng in
40mA, nhit 250C, gc qut 2 thay i t 5 550, tc qut 0,2 /pht.
II.3.2. Phng php xc nh b mt ring v phn b l xp ca cht mang
v xc tc bng phng php BET
II.3.2.1. Phng php xc nh din tch b mt ring theo BET(Sr )
Din tch b mt ring ca nhm oxit c xc nh bng phng php BET
da trn hin tng hp ph a nguyn t vi N2 77 K.
xc nh Sr bc u tin ta phi xy dng c ng ng nhit hp
ph v nh hp ph, sau xc nh theo cng thc sau:

34

Sr

xm
N . Am .10 20 m 2 / g
M

Trong :
xm lng cht hp ph n lp trn b mt 1g xc tc (g/g)
xm c th o bng cc n v khc nhau v cng thc trn cn chuyn i.
xm (cm3/g):
Sr

xm
N . Am .10 20 m 2 / g
22,4

xm (mol/g):

S r x m N . Am .10 20 m 2 / g

Am din tch ct ngang trung bnh ca phn t cht b hp ph, [A0]2

N s Avogadro (6,02.1023 phn t/mol)
M trng lng phn t cht b hp ph.
Khi dng N2 lm cht b hp ph th ta s c cng thc tnh S r n gin hn
nh sau:
Sr = 4,35. xm (m2/g)
xc nh xm ta dng phng trnh BET v tnh ra c din tnh b mt
ring.
xc nh b mt ring ta dng phng trnh BET di dng:
P / Ps
1
(C 1).P

P
x m .C x m .C.PS
x(1 )
PS

Bc u tin t gi tr P/PS v x ta thu c ng ng nhit hp ph v

nh hp ph.
Trong :
x lng cht b hp ph ti thi im ly th nghim (g/g)
35

P - p sut cn bng ti thi im

PS - p sut bo ho ca cht b hp ph ti thi im th nghim
C - hng s BET.
P / PS
x(1 P / PS )

P/PS

P/PS

Bc th hai, t phng trnh BET ta xy dng th biu din s ph thuc:

P / Ps
P

P
PS
x(1 )
PS

y l phng trnh n gin, quan h l ng thng trong gii hn nh

ca P/PS
T th ta c gc nghing to thnh v c
tg

C 1
a (1)
x m .C

ng biu din ct trc tung ti im A v ta c:

OA b

1
(2)
x m .C

T hai phng trnh (1) v (2) ta c:

xm

1
1

tg b a b

II.3.2.2. Phng php o phn b l xp

36

ng cong phn b nhit hp ph trong vng P/P 0 nh (0,05 - 0,35) c

dng o din tch b mt ring, cn li ton b ng ng nhit gii hp ph
c dng xc nh phn b kch thc l xp. Mi lin quan gia p suet hi
hp ph v bn knh mao qun c biu din qua phng trnh Kelvin nh sau:
ln(P/P0) =

.Vm.Cos
R.T.r
k

Trong :
P p sut hi bo ha nm cn bng vi cht hp ph b ngng t trong
mao qun hoc l xp.
P0 - p sut hi bo ha thng thng ca cht b hp ph.
: Sc cng b mt ca nit ti im si bng 8,85 ergs/cm2 -195,80C
Vm: Th tch mol ca nit lng bng 34,7 cm3.
: Gc tip xc ca nit, thng ly bng 00C hay cos = 1.
R: Hng s kh bng 8,314 ergs/.mol
T = 77 K
rk: Bn knh mao qun hoc l xp theo Kelvin.
Phng trnh Kelvin c th bin i thnh:
rk

4,146. A0
lg P0 / P

Gi tr rk l bn knh mao qun trong c lp cht b hp ph ngng t

p sut tng i P/P0 . Bn knh ny khng phi l bn knh thc ca l xp v
c mt lp cht hp ph trc trn thnh l xp. Trong qu trnh hp ph v gii
hp ph lp ngng t ny vn cn lu li trn thnh l xp.
Do bn knh thc l xp c xc nh theo phng trnh sau:
rp= rk + t
Trong :
rp bn knh thc ca l xp ()

37

t b dy lp hp ph v t = 3,54.V a/Vm trong 3,54 l b dy lp nit

ngng t.
V a/Vm t l i lng hp ph p sut tng i P/P 0 v i lng hp
ph n lp i vi cht rn khng xp.
Thc nghim: Cc php o din tch b mt ring v phn b l xp ca Al2O3 c thc hin trn my Micromerictics ASAP 2010.
II.3.3. Phng php phn tch nhit
y l phng php quan trng trong qu trnh nghin cu iu ch vt
liu, n cho ta c th phn on cc hin tng chuyn pha, chuyn cu trc ca
mu nghin cu thng qua s thay i trng lng ca mu theo nhit .
Nguyn tc:
Cc phng php TG, TGA, DTA, DTG l kho st s thay i trng lng
ca mu v s bin i ca cc hiu ng nhit theo nhit . Da trn cc hiu
ng thu nhit hay to nhit thu c trn gin do qu trnh tch nc, chy,
chuyn pha ta c th phn on c cc hin tng: chuyn pha, chuyn cu trc
ca mu cn nghin cu.
Nguyn tc ca phng php c th c trnh by bng s khi sau y:
A

Trong A l b phn lp chng trnh lm vic cho l nung B(gm chn tc

t nng b0C/pht, nhit ti a, kh quyn ca l nung,). Cc thong sd
c ghi bi b phn ghi thong tin C, cc thong tin ny c truyn ti b phn
x l thong tin D c ni vi my in kt qu.
Khi un nng l B theo mt chng trnh nh sn, thit b C s ghi cc
thong s t l B v biu din di dng mt hm s Y = f(t) gi l gin phn
tch nhit.
Thc nghim:
Phn tch nhit TG, TGA, DTG, DTA c tin hnh trn my NETZSCH

38

STA 409 PC/PG. Mu phn tch c ng trong chn cn Pt, nung trong mi
trng oxy, tc nng nhit 10 0C/pht, t nhit phng n nhit cui l
6000C.
II.3.4. Phng php hin vi in t truyn qua TEM
y l phng php quan trng hiu qu trong vic c trng cho cu trc
vt liu MQTB.
Nguyn tc to nh ca TEM gn ging vi knh hin vi quang hc, im
khc bit quan trng l s dng sng in t thay cho sng nh sng v thu knh
t thay cho thu knh thy tinh.
Nguyn tc:
Phng php TEM s dng sng in t c pht ra t sng phng in
t (thng dng si tungsten, Wolfram, LaB6)
Sau chm in t c hi t, thu hp nh h thu knh t v c
chiu xuyn qua mu quan st. nh s c to bng h vt knh pha sau vt,
hin ra trn mn hunh quang, hay trn phim nh, trn cc my ghi k thut s...
Tt c cc h ny c t trong bung c ht chn khng cao.
tng phn trong TEM khc so vi tng phn trong hin vi quang hc
v in t nh to ra do in t b tn x nhiu hn l do b hp th nh hin vi
quang hc.
II.3.5. Hin vi in t qut (SEM)
C s l thuyt:
Nh kh nng phng i v to nh mu rt r nt v chi tit, hin vi in
t qut (SEM) c s dng nghin cu b mt ca xc tc, xc nh kch
thc v hnh dng ca xc tc.
SEM c thc hin bng cch qut mt chm tia in t hp bc sng
khong vi A0 ln b mt mu. Khi chm in t p vo mu, trn b mt mu
pht ra cc in t th cp. Mi in t pht x ny qua in th gia tc vo phn
thu s bin i thnh mt tn hiu nh sng, chng c khuch i, a vo mng

39

li iu khin ta nh sng trn mn hnh. Mi im trn mu cho mt im

tng ng trn mn nh. sng ti trn mn nh ph thuc vo lng in t
th cp pht ra ti b thu v ph thuc vo b mt mu nghin cu.
Thc nghim:
Hnh nh knh hin vi in t qut c chp trn my JSM - 5300 v
phng i t 15 n 200.000 ln.

CHNG III : KT QU V THO LUN

III.1. HYDROXIT NHM DNG BOEMITE
Beomite l tin cht rt quan trng quyt nh s to thnh -Al2O3. Chng
ti tin hnh nghin cu cc yu t nh hng n s to thnh Beomite nhm
to ra sn phm hydroxit nhm c hm lng Beomite tinh th cao.
III.1.1. nh hng cu ch gi ho
a. nh hng cu thi gian gi ho
Tin hnh lm th nghim, sau phn ng ta tch lm 2 mu: mt mu gi
ho vi thi gian l 24h, mt mu tin hnh gi ho trong vng 10h. Kt qu
o ph XRD th hin trn hnh 19 v hnh 20

40

Mau Beomite-80C-24h

250
240
230
220
210

d=1.857

200
190

170
160

d=2.330

d=3.165

180

140
130
120

d=1.438

110
100
90

50

d=1.626

40
30
20
10

d=1.591

60

d=1.397

d=1.460

70

d=1.312

80

d=1.957

Lin (Cps)

150

0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau 3 Beomite.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 13 s - 2-Theta: 20.000 - Theta: 10.000
01-083-1505 (C) - Boehmite, syn - gamma-AlO(OH) - Y: 127.71 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 2.86840 - b 12.23230 - c 3.69490 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered

Hnh 19 : Ph XRD ca Bemit tinh th 80oC thi gian gi ha 24h

41

80

Mau Beomite thoi gian gia hoa 10h

310
300
290
280
270
260
250

d=1.850

240
230
210
200

d=2.348

d=3.186

220

180
170
160
150
140

100
90

20

d=1.720

d=1.383

30

d=1.683

40

d=1.776

d=2.726

d=2.167

50

d=2.043

60

d=1.992

70

d=1.653

80

d=1.329
d=1.316
d=1.303

110

d=1.456
d=1.440

120

d=2.221

130

d=4.365

Lin (Cps)

190

10
0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau Beomite T ghoa 18h.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 18 s - 2-Theta: 20.000 - Theta
01-083-2384 (C) - Boehmite - AlO(OH) - Y: 213.15 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 3.69360 - b 12.21400 - c 2.86790 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered - Amam (63
00-020-0011 (I) - Bayerite, syn - Al(OH)3 - Y: 45.51 % - d x by: 1. - WL: 1.5406 - Monoclinic - a 5.06200 - b 8.67100 - c 4.71300 - alpha 90.000 - beta 90.270 - gamma 90.000 - Primitive - P21/a (14) - 4 - 206.

Hnh 20 : Ph XRD ca Bemit tinh th 80oC thi gian gi ha 10h

Mu boemite c gi ha 80oC trong 24h c phn tch nhiu x tia X

(hnh 19) vi gc qut 2 thay i t 20 800. Khi xut hin cc pic mnh
nht trng vi ph chun ca Beomit l 3,165 (cng 150%); 2,330 (130%);
1,857 (170%).
Mu beomite c gi ha 80oC trong 10h c phn tch nhiu x tia X
(hnh 20) vi gc qut 2 thay i t 20 800. Ta c th thy rt r ngoi cc pic
c trng cho dng beomite cn xut hin kh nhiu cc pic khc c trng cho
tinh th bayerite ti 2,221 (cng 95%); 1,720 (cng 40%). Cn cc pic
mnh trng vi ph chun ca boemite 3,186 (cng 190%); 2,348 (cng
175%), 1,850 (cng 205%)
Qua 2 mu va ri ta c th thy gi ha 24 h mc d cng cc pic
khng ln bng cc pic gi ha 10h nhng beomite khng b ln tinh th
bayerite

42

80

b. nh hng cu nhit gi ho
Tin hnh lm th nghim, sau phn ng ta tch lm 2 mu: mt mu gi
ho iu kin nhit 80 oC, mt mu tin hnh gi ho nhit thng.
Kt qu th hin trn hnh 20 v hnh 21

Mau Beomite-80C-24h

250
240
230
220
210

d=1.857

200
190

170
160

d=2.330

d=3.165

180

140
130
120

d=1.438

110
100
90

50

d=1.626

40
30
20
10

d=1.591

60

d=1.397

d=1.460

70

d=1.312

80

d=1.957

Lin (Cps)

150

0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau 3 Beomite.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 13 s - 2-Theta: 20.000 - Theta: 10.000
01-083-1505 (C) - Boehmite, syn - gamma-AlO(OH) - Y: 127.71 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 2.86840 - b 12.23230 - c 3.69490 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered

Hnh 20 : Ph XRD ca Bemit tinh th 80oC thi gian gi ha 24h

43

80

Mau Beomite gia hoa o nhiet do thuong

1200

1100

d=2.222

1000

900

800

600

d=4.365

500

400

d=1.721

d=3.203

d=1.213

d=1.255

d=1.332

d=1.393

d=1.458
d=1.446
d=1.430

d=1.477

d=1.600

d=1.559

d=1.646

d=1.862

d=1.918

d=1.984

d=2.071

100

d=2.459

200

d=2.160

d=2.359

300

d=2.708

Lin (Cps)

700

0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau Beomite nhiet do ghoa thuong.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 12 s - 2-Theta: 20.000
00-020-0011 (I) - Bayerite, syn - Al(OH)3 - Y: 43.27 % - d x by: 1. - WL: 1.5406 - Monoclinic - a 5.06200 - b 8.67100 - c 4.71300 - alpha 90.000 - beta 90.270 - gamma 90.000 - Primitive - P21/a (14) - 4 - 206.
01-083-1505 (C) - Boehmite, syn - gamma-AlO(OH) - Y: 28.09 % - d x by: 1. - WL: 1.5406 - Orthorhombic - a 2.86840 - b 12.23230 - c 3.69490 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered

Hnh 21 : Ph XRD ca Bemit tinh th nhit thng thi gian gi ha 24h

Mu boemite c gi ha 80oC trong 24h c phn tch nhiu x tia X

(hnh 2.3a) vi gc qut 2 thay i t 20 800. Khi xut hin cc pic mnh
nht trng vi ph chun ca Beomit l 3,165 (cng 150%); 2,330 (130%);
1,857 (170%).
Mu boemite c gi ha nhit thng trong 24h c phn tch nhiu
x tia X (hnh 2.3a) vi gc qut 2 thay i t 20 80. Khi xut hin cc pic
c trng cho bayerite l ch yu, vi cng ln, chn pic hp, iu ny chng
t tinh th rt cao. Cn cc pic c trng cho boemite xut hin rt t vi cng
rt nh.
Qua hai mu trn ta thy c yu t nhit nh hng rt nhiu n qu
trnh to thnh tinh th beomite.

44

80

III.1.2. Kho st bin i ca Beomite theo nhit

a. Theo phng php TG-DSC
Trn gin TG-DSC xut hin peak thu nhit ln nht trong khong 25
2750C, nh peak ti 1530C. Trong khong nhit ny, trng lng b gim i ti
75,75%. iu ny c gii thch l do s mt nc ca mu ng thi do s
chuyn pha t Gibbsite v Bayerit sang Boehmite. Peak th hai l peak thu nhit
nh trong khong nhit 275 5000C, nh peak ti 3670C. Trong khong nhit
ny trng lng mu b gim i 3,53%, l do s chuyn pha t Boehmite
sang gamma oxit nhm.

TG /%

DSC /(mW/mg)
[1]
exo

100
Area: -47.6 J/g

90
0
Peak: 367.307
80
Area: -4768 J/g!

-0.5

70
Mass Change: -75.75 %
60

-1.0
50

40

-1.5

30
Mass Change: -3.53 %
Peak: 153.485

Mass Change: -0.92 %

[1] -2.0

20
100

200

300

400

500

600

700

800

900

1000

Administrator 23-05-2008 13:35

Instrument:
File:
Project:
Identity:
Date/Time:
Laboratory:
Operator:

NETZSCH STA 409 PC/PG

80-2008 Boehmit M1.s...
HUT
Boehmite
5/22/2008 2:25:51 PM
PCM
T.D.Duc

Sample:
Reference:
Material:
Correction File:
Temp.Cal./Sens. Files:
Range:
Sample Car./TC:

80-2008 BoehmitM1, 90.000 mg

Al2O3,0.000 mg
Boehmite
Calib new.tsv / Calib ngay 10 5 2007.esv
30/10.00(K/min)/1000
DSC(/TG) HIGH RG 2 / S

Mode/Type of Meas.:
Segments:
Crucible:
Atmosphere:
TG Corr./M.Range:
DSC Corr./M.Range:
Remark:

DSC-TG / Sample
1/1
DSC/TG pan Al2O3
O2/30 / N2/10
000/30000 mg
000/5000 V

Hnh 22: Gin TG-DSC ca mu boehmit t A_A

b. Theo phng php Ph FTIR
i vi mu mesopore -Al2O3 tng hp vi cht HBM, thy r s
phn hy ca cht HBM, sn phm sau khi sy 110, 180 oC, v nung 230

45

v 500oC c phn tch hng ngoi. Kt qu ph hng ngoi c trnh by

trong hnh sau.
110oC

hu yen 1

13

12

20 94.7

11

10

%T

28 49.4

16 44.6

13 84.4

35 00.6

2
4 000

3 500

61 7.7

11 16.2

29 16.7

3 000

2 500

2 000

1 500

1 000

5 00

W ave num bers (c m-1 )

40

180oC

18 0oC Al2O3

87 7.0

35

22 25.4

72 5.4

21 09.1

24 27.8

-5
4 000

48 1.7
61 6.2
63 8.0

13 84.2

11 14.8

34 65.3

16 50.1

10

83 5.5

99 7.0

17 89.3

29 57.7

15

24 75.6

%T

29 17.5

20

28 50.0

38 51.0

25

22 96.6

27 65.0

23 58.8

30

3 500

3 000

2 500

2 000

W ave num bers (c m-1 )

46

1 500

1 000

5 00

20

4 000

3 500

14 28.4

3 000
2 000

50

40

2 500

W ave num bers (c m-1 )

47

2 000

1 500

1 500

61 5.1

2 500

83 5.5

99 4.5

3 000

-5
63 8.1

61 6.2

11 27.7

13 84.3

11 53.8

3 500

1 000

48 1.2

83 5.7

15 90.0

17 89.2

72 5.9

24 76.0

21 09.4

22 24.9

24 27.8

28 50.0

29 17.5

25

13 53.7

16 44.7

4 000

17 89.1

20
29 58.0

27 65.2

21 80.7

30

20 96.7

24 27.4

10
34 54.6

%T
45

35 00.5

%T

230oC
23 0oC

40

35

15

W ave num bers (c m-1 )

1 000
5 00

500oC
60
50 0oC

55

45

35

30

25

5 00

2096.7

55

500oC
180oC
230oC
110oC

2427.4

60

50

4000

3500

725.9
615.1

835.5

617.7

481.7
481.2

835.5835.7

997.0

1153.8

1428.4

1353.7

1644.7
1789.2

1500

725.4

994.5

2500
2000
Wavenumbers (cm-1)

1789.3

2180.7
2225.4
2224.9

2109.4
2109.1

2358.8

2475.6

2296.6

2476.0
2427.8

2850.0

2765.0

2850.0

3000

1644.61650.1
1590.0

2849.4

10

2094.7

3465.3 3454.6

15

2916.7

20

3500.5

25

2957.7 2958.0
2917.5 2917.5

30
3851.0

%T

35

2427.8

2765.2

40

877.0

1789.1

45

1000

500

Hnh 23. Ph FTIR ca cc mu oxit nhm tng hp vi cht HBM

cc nhit sy nung khc nhau
Khi nung n 230oC, cht hot n g b m t vn cha b phn hy ht, th
hi n trn ph FTIR ti cc s sng 2875 2950 cm-1 c trng cho dao ng ca
nhm -CH3; ti 2885 2865 cm-1 c trng cho dao ng ca nhm C-H; ti 485
cm-1 c trng cho alkan mch thng v ti s sng 1650 cm-1 c trng cho dao
ng bt i xng ca nhm COO-. Khi nung n 500oC, cc pic c trng cho
u hydrocacbon khng phn cc khng cn na, chng t cht HBM b
phn hy ht
III.2. VT LIU MQTB -Al2O3
III.2.1.. nh hng cu ch nung
Ch sy - nung l m t trong cc yu t quan trng nht quyt nh s
hnh thnh ca -Al2O3. cc nhi t nung khc nhau oxit nhm d dng b
chuyn thnh cc pha vi cu trc khc nhau. Trong cc dng th hnh ca oxit
nhm, th ch c -Al2O3 hay c s dng trong hp ph v xc tc.

48

Bng thc nghim cc tc gi a ra s chuyn pha theo nhit th

hin trn hnh 24.
Nhit (oC)

Hnh 24- S chuyn pha theo nhit ca cc hydroxit v oxit nhm

Theo gin ny ta nhn thy cc im c bit sau:
-

thu c - Al2O3 c hm lng pha tinh th cao, iu kin tin

quyt l ch to c boehmit c hm lng pha tinh th cao.

Ti nhit 180oC c s chuyn pha t bayerit sang boehmit v ti

nhit 230oC c s chuyn pha t gibbsit sang boehmit cho nn cn
c ch nhit sy, nung hp l nng cao hm lng pha tinh
th ca boehmit tc cng chnh l nng cao hm lng pha tinh th
ca - Al2O3.

T nhit khong 800oC c s chuyn pha ca - Al2O3 sang dng

- Al2O3, do vy khi s dng cng nh trong qu trnh tng hp khng nn nung
nhit cao qu nh vy s lm gim hm lng tinh th ca - Al2O3.
a. Nung theo ch c giai on 230oC
ng ng nhi t hp ph v phn b mao qun trung bnh ca mu Al2O3 vi ch nung c giai on 230oC

49

Hnh 25. ng ng nhi t hp ph v phn b mao qun ca mu Al2O3 m t sau khi nung 500oC ch c giai on 230oC
ng ng nhi t hp ph ca mu A_A c vng tr trong khong p sut
tng i P/Po = 0,45 1, theo phn loi ca IUPAC y l ng ng nhi t c
trng cho v t li u mao qun trung bnh c tr t t. Di n tch b m t BET tnh
c l 264.2 m2/g. ng knh mao qun t p trung ti 10 nm
b. Nung theo ch khng c giai on 2300C
ng ng nhi t hp ph v phn b mao qun trung bnh ca mu Al2O3 tng hp vi cht hot ng b m t sau khi nung tho ch khng c
giai on 230oC c trnh by trong hnh 26 .

50

Hnh 26. ng ng nhi t hp ph v phn b mao qun ca mu Al2O3 sau khi nung 500oC ch nung khng c giai on 230oC
ng ng nhi t hp ph ca mu A_A c vng tr trong khong p sut
tng i P/Po = 0,45 1, theo phn loi ca IUPAC y l ng ng nhi t c
trng cho v t li u mao qun trung bnh c tr t t. Di n tch b m t BET tnh
c l 323,5 m2/g. ng knh mao qun trung bnh l 6,9 nm, ng knh mao
qun t p trung ti 4 v 6 nm
III.2.1.. nh hng cu tc nung
nghin cu nh hng ca tc nung, ta tin hnh nung cc mu
nhng tc gia nhit 50C/ph, 100C/ph, 300C/ph. Kt qu c phn tch bi ph
XRD
Mau gama-Al2O3-500C-v=5C/ph

250
240
230
220

190

d=2.288

180

d=1.406

d=2.430

200

d=1.969

210

170
160

140
130
120
110

d=1.527

Lin (Cps)

150

100
90
80
70
60
50
40
30
20
10
0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau Gama-Al2O3-500C-5C-ph.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 19 s - 2-Theta: 20.000 00-004-0858 (D) - Aluminum Oxide - gamma-Al2O3 - Y: 83.16 % - d x by: 1. - WL: 1.5406 -

51

80

Hnh 27 : Ph XRD ca -Al2O3 khi nung boemite n 500oC vi tc nung

50C/ph
Ph XRD ca - Al2O3 khi nung boemite vi tc nung 50C/ph c gc
qut 2 thay i t 20 800, khi xut hin cc pic mnh nht trng vi ph
chun ca - Al2O3 l 2,430 (cng 175%), 2,28 (cng 155%), 1,969
(180%), 1,406 (180%)

Mau gama-Al2O3-v=10C/ph

250
240
230
220
210

180

d=2.251

170

d=1.403

d=2.446

190

160
150
140
130
120
110

d=1.551

Lin (Cps)

d=1.973

200

100
90
80
70
60
50
40
30
20
10
0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau Gama-Al2O3-v=10C-ph.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 12 s - 2-Theta: 20.000 - Th
00-004-0858 (D) - Aluminum Oxide - gamma-Al2O3 - Y: 81.16 % - d x by: 1. - WL: 1.5406 -

Hnh 28 : Ph XRD ca -Al2O3 khi nung boemite n 500oC vi tc nung

100C/ph

52

80

Ph XRD ca - Al2O3 khi nung boemite vi tc nung 100C/ph c gc

qut 2 thay i t 20 800, khi xut hin cc pic mnh nht trng vi ph
chun ca - Al2O3 l 2,446 (cng 1170%), 2,251 (cng 140%), 1,973
(170%), 1,403 (180%)

Mau gama-Al2O3-500C-v=30C/ph

250
240
230
220

190

d=2.299

180

d=1.400

200

d=1.985
d=1.961

d=2.427

210

170
160

140
130
120
110

d=1.546

Lin (Cps)

150

100
90
80
70
60
50
40
30
20
10
0
20

30

40

50

60

70

2-Theta - Scale
File: Hoang BK mau Gama-Al2O3-500C-30C-ph.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 18 s - 2-Theta: 20.000
00-004-0858 (D) - Aluminum Oxide - gamma-Al2O3 - Y: 83.93 % - d x by: 1. - WL: 1.5406 -

Hnh 29 : Ph XRD ca -Al2O3 khi nung boemite n 500oC vi tc nung

300C/ph
Ph XRD ca - Al2O3 khi nung boemite vi tc nung 300C/ph c gc
qut 2 thay i t 20 800, khi xut hin cc pic mnh nht trng vi ph
chun ca - Al2O3 l 2,4270 (cng 175%), 2,299 (cng 150%), 1,961
(175%), 1,400 (180%)
T nhng mu nghin cu trn ta thy khi nung n 500 oC tt c boemite
chuyn thnh dng gama oxit nhm. Khi thay i tc gia nhit khng lm
thay i ng k tinh th ca gama oxit nhm.
53

80

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