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Vật Liệu Mao Quản Trung Binh Al2O3
Vật Liệu Mao Quản Trung Binh Al2O3
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 -AL
2
O
3
: .................................................... 8
I.2.1. Cu trc ca -Al
2
O
3
:...................................................................................... 8
I.2.2. Tnh cht b mt ca -Al
2
O
3
: ..................................................................... 11
I.2.3. Cu trc xp ca -Al
2
O
3
: ............................................................................ 11
I.3. VT LIU MESOPOROUS V MESOPOROUS -Al
2
O
3
............................. 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 Al
2
O
3
ni chung. .................................................................. 25
I.4.2. ng dng ca - Al
2
O
3
. ............................................................................... 27
I.4.3. Trin vng pht trin sn xut -Al
2
O
3
...................................................... 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 -Al
2
O
3
.............................................................................. 47
III.2.1.. nh hng cu ch nung ..................................................................... 47
III.2.1.. nh hng cu tc nung ..................................................................... 50
2
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 phNm 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 -Al
2
O
3
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 Nm trong ch bin kh thin nhin, cht hp
ph, cht mang, xc tc cho ngnh tng hp v c v hu c.
3
Trong phm vi n ny, chng ti tin hnh tng hp vt liu -Al
2
O
3
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 -Al
2
O
3
MQTB vi din tch
b ring mt ln v s phn b mao qun hp.
4
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
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 230
0
C th 2 phn t nc tch ra khi tinh th Gibbsit v
Gibbsit chuyn ho thnh Bemit
100 200 300 400 500 600 700 800 900 1000 1100
0
C
Eta Alpha Theta
Diaspore Alpha
Gibbsit Chi Alpha Kappa
Bemit
Bayerit
Alpha Theta Delta Gamma
5
Nung n 500
0
C 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 180200
o
C 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 phNm khc vi Bayerit v
Nordstandit.Trong chn khng, nhit thp 3 dng ca nhm tri hydroxit phn
hu to sn phNm v nh hnh,sau nhit cao hn bin i thnh
Al
2
O
3
, Al
2
O
3
, v Al
2
O
3
. Diaspor l nhm hydroxit duy nht phn hu trc
tip ra Al
2
O
3
T gin ta thy ti nhit thp ch c Beomite khi nung mi to ra
c -Al
2
O
3.
Cn cc dng nhm hydroxyt khc khi nung cc iu kin nhit
khc nhau to ra cc dng oxit nhm khc nh - Al
2
O
3
, - Al
2
O
3,
- Al
2
O
3
;-
Al
2
O
3
;- Al
2
O
3
v - Al
2
O
3
. Chnh v vy ta s ch nghin cu tnh cht v cu
trc ca Beomite v -Al
2
O
3
I.1.2. Cu trc v tnh cht ca Beomite
A. Tinh th beomite
Beomite c cng thc ha hc Al
2
O
3
.H
2
O = 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)
6
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 A
o
b = 12,214 + 0,0001 A
o
c = 2,8679 + 0,0003 A
o
Khong cch ca cc nguyn t c trch trong bng di
7
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 Al
3+
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
o
C 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
2
O
3
. xH
2
O 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.
8
I.2. CU TRC V TNH CHT CA -AL
2
O
3
:
Trc khi cp n vt liu -Al
2
O
3
MQTB, ta hy tm hiu v cu trc
v tnh cht chung ca -Al
2
O
3
.
I.2.1. Cu trc ca -Al
2
O
3
:
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)
Hnh 3: Cu trc khi ca - Al
2
O
3
.
Cc cation kim loi trong Al
3+
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 Al
3+
trong trng hp
ny nm v tr tm bt din
1
1
1 1 1
1 1
1 1
1
2
2 2
2
2
2
3
3
3
9
Hnh 4: S phn b ca Al
3+
trong mng khng gian.
Lp oxy th hai ca oxit trong v tr 2 phn b trn Al
3+
. Nu tip tc sp
xp bng phng php ny th mt ion Al
3+
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 Al
3+
Hnh 5: V tr ion Al
3+
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
Al
3+
1
1
1 1 1
1 1
1 1
1
O
2-
Al
3+
10
ion nm trung tm, ng thi khi bt din kt hp vi khi t din v to
khong khng gian cho cc cation b. Al
3+
c th vo khi bt din v t din.
Hnh 6: Hai lp u tin ca tinh th - Al
2
O
3
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 -Al
2
O
3
v - Al
2
O
3
c th vit tng ng: (H
1/2
Al
1/2
)Al
2
O
4
hay Al(H
1/2
Al
3/4
)O
4
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 - Al
2
O
3
v - Al
2
O
3
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. - Al
2
O
3
cha ion Al
3+
trong khi t din ln hn trong - Al
2
O
3
.
- Al
2
O
3
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
th 2, ion Al
3+
ch phn b trong l trng bt din. Trong - Al
2
O
3
, lp th 2 ion
Al
3+
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.
11
I.2.2. Tnh cht b mt ca -Al
2
O
3
:
Tnh cht ha hc b mt ca -Al
2
O
3
lin quan trc tip n tnh cht xc
tc v hp ph ca chng. -Al
2
O
3
hot tnh, ngoi Al
2
O
3
tinh khit thng cha
t 1 5% nc. Ph thuc vo iu kin ch to, trong -Al
2
O
3
c th cha oxit
kim loi kim, oxit st, ion sunfat. Cc tp cht ny c nh hng n tnh cht
xc tc ca -Al
2
O
3
. V d nh s c mt ca SO
4
2-
v mt s anion khc lm tng
axit ca -Al
2
O
3
.
Ph thuc vo nhit , -Al
2
O
3
c th hp ph nc dng phn t H
2
O
hoc dng ion OH
-
. Khi tip xc vi hi nc nhit thng, -Al
2
O
3
hp ph
nc dng phn t H
2
O 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
0
C.
Bng phng php ph hng ngoi chng minh c rng, nhit thp trn
b mt -Al
2
O
3
tn ti nc dng khng phn ly, khi sy mu 300
0
C 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
2
O, nhng ngay c
nhit 800 1000
0
C 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
I.2.3. Cu trc xp ca -Al
2
O
3
:
A. Din tch b mt ring:
-Al
2
O
3
i t gel Bemite c din tch b mt vo khong 150 250m
2
/g,
cha nhiu l xp c ng knh t 30120A
0
v th tch l xp t 0,51 cm
3
/g .
12
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 -Al
2
O
3
:
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 A
0
. 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 cm
3
/g .
C. Tnh axit ca -Al
2
O
3
:
Ph thuc vo mc dehidrat ha, trn b mt -Al
2
O
3
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
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.
13
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
-
OH
-
OH
-
OH
-
OH
-
OH
-
Al
3+
Al
3+
Al
3+
Al
3+
sang b mt c cha Cl
-
v OH
-
(v d nh hot ha b mt bng HCl)
Cl
-
OH
-
Cl
-
OH
-
Cl
-
OH
-
Al
3+
Al
3+
Al
3+
Al
3+
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. -Al
2
O
3
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 -Al
2
O
3
I.3.1. Gii thiu chung v vt liu MQTB
-Al
2
O
3
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,
14
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,
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
15
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: ZrO
2
, TiO
2
I.3.3. Cc dng ng ng nhit hp ph v nh hp ph ca vt liu
MQTB
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
16
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.
Hnh 8: Ba dng ng ng nhit hp ph v nh hp ph ca vt liu MQTB
a) b) c)
Hnh 9: Ba dng mao qun ph bin ca vt liu MQTB
a) b) c)
17
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 -
C
12
H
25
N(CH
3
)
3
Br, 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.
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
18
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
phNm mong mun v c gi thnh va phi.
Cc loi dung mi thng c s dng trong qu trnh tng hp vt liu
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
19
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
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
20
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 (S
0
I
0
) 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 MCM-
41. 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
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
21
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
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
22
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
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
23
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
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
24
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
C
16
H
33
(CH
3
)
3
NBr.
Bc u tin t gi tr P/P
S
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)
P - p sut cn bng ti thi im
P
S
- p sut bo ho ca cht b hp ph ti thi im th nghim
C - hng s BET.
) / 1 (
/
S
S
P P x
P P
x
A
P/P
S
P/P
S
36
Bc th hai, t phng trnh BET ta xy dng th biu din s ph thuc:
S
S
s
P
P
P
P
x
P P
) 1 (
/
y l phng trnh n gin, quan h l ng thng trong gii hn nh
ca P/P
S
T th ta c gc nghing to thnh v c
a
C x
C
tg
m
=
=
.
1
(1)
ng biu din ct trc tung ti im A v ta c:
C x
b OA
m
.
1
= = (2)
T hai phng trnh (1) v (2) ta c:
b a b tg
x
m
+
=
+
=
1 1
II.3.2.2. Phng php o phn b l xp
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/P
0
) =
k
R.T.r
.Cos
m
.V
Trong :
P p sut hi bo ha nm cn bng vi cht hp ph b ngng t trong
mao qun hoc l xp.
P
0
- 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/cm
2
-195,8
0
C
37
V
m
: Th tch mol ca nit lng bng 34,7 cm3.
: Gc tip xc ca nit, thng ly bng 0
0
C hay cos = 1.
R: Hng s kh bng 8,314 ergs/.mol
T = 77 K
r
k
: Bn knh mao qun hoc l xp theo Kelvin.
Phng trnh Kelvin c th bin i thnh:
( ) P P
A
r
k
/ lg
. 146 , 4
0
0
=
Gi tr r
k
l bn knh mao qun trong c lp cht b hp ph ngng t
p sut tng i P/P
0
. 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:
r
p
= r
k
+ t
Trong :
r
p
bn knh thc ca l xp ()
t b dy lp hp ph v t = 3,54.V
a
/V
m
trong 3,54 l b dy lp nit
ngng t.
V
a
/V
m
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 -
Al
2
O
3
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
38
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:
Trong A l b phn lp chng trnh lm vic cho l nung B(gm chn
tc t nng b
0
C/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
STA 409 PC/PG. Mu phn tch c ng trong chn cn Pt, nung trong mi
trng oxy, tc nng nhit 10
0
C/pht, t nhit phng n nhit cui l
600
0
C.
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)
A B C D
39
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 A
0
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
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.
40
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 -Al
2
O
3
. Chng
ti tin hnh nghin cu cc yu t nh hng n s to thnh Beomite nhm
to ra sn phNm 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
Mau Beomite-80C-24h
01-083-1505 (C) - Boehmi te, syn - gamma-Al O(OH) - Y: 127.71 % - d x by: 1. - WL: 1.5406 - Orthorhombi c - a 2.86840 - b 12.23230 - c 3.69490 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered
File: Hoang BK mau 3 Beomite.raw - Type: Locked Coupl ed - 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
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
2-Theta - Scale
20 30 40 50 60 70 80
d
=
3
.
1
6
5
d
=
2
.
3
3
0
d
=
1
.
9
5
7
d
=
1
.
8
5
7
d
=
1
.
6
2
6
d
=
1
.
5
9
1
d
=
1
.
4
3
8
d
=
1
.3
1
2
d
=
1
.
3
9
7 d
=
1
.
4
6
0
Hnh 19 : Ph XRD ca Bemit tinh th 80
o
C thi gian gi ha 24h
41
Mau Beomite thoi gian gia hoa 10h
00-020-0011 (I) - Bayeri te, syn - Al (OH)3 - Y: 45.51 % - d x by: 1. - WL: 1.5406 - Monocli nic - a 5.06200 - b 8.67100 - c 4.71300 - alpha 90.000 - beta 90.270 - gamma 90.000 - Primitive - P21/a (14) - 4 - 206.
01-083-2384 (C) - Boehmi te - AlO(OH) - Y: 213.15 % - d x by: 1. - WL: 1.5406 - Orthor hombic - a 3.69360 - b 12.21400 - c 2.86790 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered - Amam (63
File: Hoang BK mau Beomite T ghoa 18h.r aw - 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
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
2-Theta - Scale
20 30 40 50 60 70 80
d
=
4
.
3
6
5
d
=
3
.
1
8
6
d
=
2
.7
2
6
d
=
2
.3
4
8
d
=
2
.
2
2
1
d
=
2
.
1
6
7
d
=
2
.
0
4
3
d
=
1
.
9
9
2
d
=
1
.
8
5
0
d
=
1
.
7
2
0
d
=
1
.
6
8
3
d
=
1
.
6
5
3
d
=
1
.
4
5
6
d
=
1
.
4
4
0
d
=
1
.
3
8
3
d
=
1
.
3
2
9
d
=
1
.
3
0
3
d
=
1
.
3
1
6
d
=
1
.
7
7
6
Hnh 20 : Ph XRD ca Bemit tinh th 80
o
C thi gian gi ha 10h
Mu boemite c gi ha 80
o
C trong 24h c phn tch nhiu x tia X
(hnh 19) vi gc qut 2 thay i t 20 80
0
. Khi xut hin cc pic mnh
nht trng vi ph chuNn ca Beomit l 3,165 (cng 150%); 2,330 (130%);
1,857 (170%).
Mu beomite c gi ha 80
o
C trong 10h c phn tch nhiu x tia X
(hnh 20) vi gc qut 2 thay i t 20 80
0
. 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 chuNn 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
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
o
C, mt mu tin hnh gi ho nhit thng.
Kt qu th hin trn hnh 20 v hnh 21
Mau Beomite-80C-24h
01-083-1505 (C) - Boehmi te, syn - gamma-Al O(OH) - Y: 127.71 % - d x by: 1. - WL: 1.5406 - Orthorhombi c - a 2.86840 - b 12.23230 - c 3.69490 - alpha 90.000 - beta 90.000 - gamma 90.000 - Base-centered
File: Hoang BK mau 3 Beomite.raw - Type: Locked Coupl ed - 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
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
2-Theta - Scale
20 30 40 50 60 70 80
d
=
3
.
1
6
5
d
=
2
.
3
3
0
d
=
1
.
9
5
7
d
=
1
.
8
5
7
d
=
1
.
6
2
6
d
=
1
.
5
9
1
d
=
1
.
4
3
8
d
=
1
.3
1
2
d
=
1
.
3
9
7 d
=
1
.
4
6
0
Hnh 20 : Ph XRD ca Bemit tinh th 80
o
C thi gian gi ha 24h
43
Mau Beomite gia hoa o nhiet do thuong
01-083-1505 (C) - Boehmi te, 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
00-020-0011 (I) - Bayeri te, syn - Al(OH)3 - Y: 43.27 % - d x by: 1. - WL: 1.5406 - Monocli nic - a 5.06200 - b 8.67100 - c 4.71300 - alpha 90.000 - beta 90.270 - gamma 90.000 - Primitive - P21/a (14) - 4 - 206.
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
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
2-Theta - Scale
20 30 40 50 60 70 80
d
=
4
.
3
6
5
d
=
3
.
2
0
3
d
=
2
.
7
0
8
d
=
2
.
4
5
9
d
=
2
.
3
5
9
d
=
2
.
2
2
2
d
=
2
.
1
6
0
d
=
2
.
0
7
1
d
=
1
.
9
8
4
d
=
1
.
9
1
8
d
=
1
.
8
6
2
d
=
1
.
7
2
1
d
=
1
.
6
4
6
d
=
1
.
6
0
0
d
=
1
.
5
5
9
d
=
1
.
4
7
7
d
=
1
.
4
5
8
d
=
1
.
4
4
6
d
=
1
.
4
3
0
d
=
1
.
3
9
3
d
=
1
.
3
3
2
d
=
1
.
2
5
5
d
=
1
.2
1
3
Hnh 21 : Ph XRD ca Bemit tinh th nhit thng thi gian gi ha 24h
Mu boemite c gi ha 80
o
C trong 24h c phn tch nhiu x tia X
(hnh 2.3a) vi gc qut 2 thay i t 20 80
0
. Khi xut hin cc pic mnh
nht trng vi ph chuNn 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
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
275
0
C, nh peak ti 153
0
C. 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 275 500
0
C, nh peak ti 367
0
C. Trong khong nhit
ny trng lng mu b gim i 3,53%, l do s chuyn pha t Boehmite
sang gamma oxit nhm.
100 200 300 400 500 600 700 800 900 1000
-2.0
-1.5
-1.0
-0.5
0
DSC /(mW/mg)
20
30
40
50
60
70
80
90
100
TG /%
Area: -4768 J/g!
Area: -47.6 J/g
Peak: 153.485
Peak: 367.307
Mass Change: -75.75 %
Mass Change: -3.53 %
Mass Change: -0.92 %
[1]
[1]
exo
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
Administrator 23-05-2008 13:35
Hnh 22: Gin TG-DSC ca mu boehmit t A_A
b. Theo phng php Ph FTIR
i vi mu mesopore -Al
2
O
3
tng hp vi cht HBM, thy r s
phn hy ca cht HBM, sn phNm sau khi sy 110, 180
o
C, v nung 230
45
v 500
o
C c phn tch hng ngoi. Kt qu ph hng ngoi c trnh by
trong hnh sau.
110oC
180oC
6
1
7
.7
1
1
1
6
.2
1
3
8
4
.4
1
6
4
4
.6
2
0
9
4
.7
2
8
4
9
.4
2
9
1
6
.7
3
5
0
0
.6
huyen 1
2
3
4
5
6
7
8
9
10
11
12
13
%
T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
4
8
1
.7
6
1
6
.2
6
3
8
.0
7
2
5
.4
8
3
5
.5
8
7
7
.0
9
9
7
.0
1
1
1
4
.8
1
3
8
4
.2
1
6
5
0
.1
1
7
8
9
.3
2
1
0
9
.1
2
2
2
5
.4
2
2
9
6
.6
2
3
5
8
.8
2
4
2
7
.8
2
4
7
5
.6
2
7
6
5
.0
2
8
5
0
.0
2
9
1
7
.5
2
9
5
7
.7
3
4
6
5
.3
3
8
5
1
.0
180oC Al2O3
-5
0
5
10
15
20
25
30
35
40
%
T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
46
230oC
500oC
4
8
1
.2
6
1
6
.2
6
3
8
.1
7
2
5
.9
8
3
5
.7
1
1
2
7
.7
1
3
8
4
.3
1
5
9
0
.0
1
7
8
9
.2
2
1
0
9
.4
2
1
8
0
.7
2
2
2
4
.9
2
4
2
7
.8
2
4
7
6
.0
2
7
6
5
.2
2
8
5
0
.0
2
9
1
7
.5
2
9
5
8
.0
3
4
5
4
.6
230oC
-5
0
5
10
15
20
25
30
35
40
45
%
T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
6
1
5
.1
8
3
5
.5
9
9
4
.5
1
1
5
3
.8
1
3
5
3
.7
1
4
2
8
.4
1
6
4
4
.7
1
7
8
9
.1
2
0
9
6
.7 2
4
2
7
.4
3
5
0
0
.5
500oC
20
25
30
35
40
45
50
55
60
%
T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
47
Hnh 23. Ph FTIR ca cc mu oxit nhm tng hp vi cht HBM
cc nhit sy nung khc nhau
Khi nung n 230
o
C, cht hot ng b mt vn cha b phn hy ht, th
hin trn ph FTIR ti cc s sng 2875 2950 cm
-1
c trng cho dao ng ca
nhm -CH
3
; 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 500
o
C, 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 -Al
2
O
3
III.2.1.. nh hng cu ch nung
Ch sy - nung l mt trong cc yu t quan trng nht quyt nh s
hnh thnh ca -Al
2
O
3
. cc nhit 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 -Al
2
O
3
hay c s dng trong hp ph v xc tc.
615.1
835.5
994.5
1153.8
1353.7
1428.4
1644.7
1789.1
2096.7
2427.4
3500.5
481.7
725.4
835.5
877.0
997.0
1650.1
1789.
2109.1
2225.4
2296.6
2358.8
2427.8
2475.6
2765.0
2850.0
2917.5
2957.7
3465.3
3851.0
617.7
1644.6
2094.7
2849.4
2916.7
481.2
725.9
835.7
1590.0
1789.
2109.4
2180.7
2224.9
2427.8
2476.0
2765.2
2850.0
2917.5
2958.0
3454.6
500oC
180oC
230oC
110oC
5
10
15
20
25
30
35
40
45
50
55
60
%T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
48
Bng thc nghim cc tc gi a ra s chuyn pha theo nhit th
hin trn hnh 24.
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 - Al
2
O
3
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 180
o
C c s chuyn pha t bayerit sang boehmit v ti
nhit 230
o
C 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 - Al
2
O
3
.
T nhit khong 800
o
C c s chuyn pha ca - Al
2
O
3
sang dng
- Al
2
O
3
,
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 - Al
2
O
3
.
a. Nung theo ch c giai on 230oC
ng ng nhit hp ph v phn b mao qun trung bnh ca mu -
Al
2
O
3
vi ch nung c giai on 230
o
C
Nhit (
o
C)
49
Hnh 25. ng ng nhit hp ph v phn b mao qun ca mu -
Al
2
O
3
mt sau khi nung 500
o
C ch c giai on 230
o
C
ng ng nhit hp ph ca mu A_A c vng tr trong khong p sut
tng i P/P
o
= 0,45 1, theo phn loi ca IUPAC y l ng ng nhit c
trng cho vt liu mao qun trung bnh c trt t. Din tch b mt BET tnh c
l 264.2 m
2
/g. ng knh mao qun tp trung ti 10 nm
b. Nung theo ch khng c giai on 230
0
C
ng ng nhit hp ph v phn b mao qun trung bnh ca mu -
Al
2
O
3
tng hp vi cht hot ng b mt sau khi nung tho ch khng c
giai on 230
o
C c trnh by trong hnh 26 .
50
Hnh 26. ng ng nhit hp ph v phn b mao qun ca mu -
Al
2
O
3
sau khi nung 500
o
C ch nung khng c giai on 230
o
C
ng ng nhit hp ph ca mu A_A c vng tr trong khong p sut
tng i P/P
o
= 0,45 1, theo phn loi ca IUPAC y l ng ng nhit c
trng cho vt liu mao qun trung bnh c trt t. Din tch b mt BET tnh c
l 323,5 m
2
/g. ng knh mao qun trung bnh l 6,9 nm, ng knh mao qun
tp 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 5
0
C/ph, 10
0
C/ph, 30
0
C/ph. Kt qu c phn tch bi ph
XRD
Mau gama-Al2O3-500C-v=5C/ph
00-004-0858 (D) - Aluminum Oxide - gamma-Al 2O3 - Y: 83.16 % - d x by: 1. - WL: 1.5406 -
File: Hoang BK mau Gama-Al 2O3-500C-5C-ph.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step ti me: 0.8 s - Temp.: 25 C (Room) - Time Started: 19 s - 2-Theta: 20.000 -
L
i
n
(
C
p
s
)
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
2-Theta - Scale
20 30 40 50 60 70 80
d
=
1
.
4
0
6
d
=
1
.
5
2
7
d
=
1
.
9
6
9
d
=
2
.
2
8
8
d
=
2
.
4
3
0
51
Hnh 27 : Ph XRD ca -Al
2
O
3
khi nung boemite n 500
o
C vi tc nung
5
0
C/ph
Ph XRD ca - Al
2
O
3
khi nung boemite vi tc nung 5
0
C/ph c gc
qut 2 thay i t 20 80
0
, khi xut hin cc pic mnh nht trng vi ph
chuNn ca - Al
2
O
3
l 2,430 (cng 175%), 2,28 (cng 155%), 1,969
(180%), 1,406 (180%)
Mau gama-Al2O3-v=10C/ph
00-004-0858 (D) - Aluminum Oxide - gamma-Al2O3 - Y: 81.16 % - d x by: 1. - WL: 1.5406 -
File: Hoang BK mau Gama-Al 2O3-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
L
i
n
(
C
p
s
)
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
2-Theta - Scale
20 30 40 50 60 70 80
d
=
1
.
4
0
3
d
=
1
.
9
7
3
d
=
1
.
5
5
1
d
=
2
.
4
4
6
d
=
2
.
2
5
1
Hnh 28 : Ph XRD ca -Al
2
O
3
khi nung boemite n 500
o
C vi tc nung
10
0
C/ph
Ph XRD ca - Al
2
O
3
khi nung boemite vi tc nung 10
0
C/ph c gc
qut 2 thay i t 20 80
0
, khi xut hin cc pic mnh nht trng vi ph
52
chuNn ca - Al
2
O
3
l 2,446 (cng 1170%), 2,251 (cng 140%), 1,973
(170%), 1,403 (180%)
Mau gama-Al2O3-500C-v=30C/ph
00-004-0858 (D) - Aluminum Oxide - gamma-Al 2O3 - Y: 83.93 % - d x by: 1. - WL: 1.5406 -
File: Hoang BK mau Gama-Al 2O3-500C-30C-ph.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25 C (Room) - Ti me Started: 18 s - 2-Theta: 20.000
L
i
n
(
C
p
s
)
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
2-Theta - Scale
20 30 40 50 60 70 80
d
=
1
.4
0
0
d
=
1
.
5
4
6
d
=
1
.
9
8
5
d
=
1
.
9
6
1
d
=
2
.
2
9
9
d
=
2
.
4
2
7
Hnh 29 : Ph XRD ca -Al
2
O
3
khi nung boemite n 500
o
C vi tc nung
30
0
C/ph
Ph XRD ca - Al
2
O
3
khi nung boemite vi tc nung 30
0
C/ph c gc
qut 2 thay i t 20 80
0
, khi xut hin cc pic mnh nht trng vi ph
chuNn ca - Al
2
O
3
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
o
C 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.