1

TS. Ng Thanh An
XC TC AXIT BAZ RN
Thng 12 nm 2010
2
Bng cch no bit mt oxit c tnh axit/baz
Dng IEP c khng???
OXIT N
3
OXIT N
4
Ca (z = 20)
Mg (z = 12)
Ba (z = 56)
Al (z = 13)
Ti (z = 22)
Zr (z = 40)
OXIT N
5
MgO: xc tc baz
Ti sao???
OXIT N
6
ZrO
2
Va c tnh axit yu va c tnh baz yu
Lc axit mnh nht ca ZrO
2
khi nung trong khng kh 773 K,
trong 3h l H
o
= +1.5.
axit H
o
e +1.5 l 0.06 mmol/g v H
o
e +4.0 l 0.28 mmol/g
C tnh axit yu, ch yu l Lewis, 1 phn nh l Bronsted
OXIT N
7
OXIT N
ZrO
2
8
Al
2
O
3
c s dng rng ri trong cng nghip xc tc bi v:
- N l cht mang rt hiu qu
- N cng l 1 cht xc tc
Alumina xp thu c t qu trnh hydrat c kim sot aluminum
hydroxide (Al(OH)
3
= Al
2
O
3
.3H
2
O).
OXIT N
9
Aluminum hydroxide c th tn ti 1 vi dng tinh th nh l
gibbsite (hydrargillite), bayerite, v nordstrandite (tt c u l vt liu
khng xp)
X l nhit gibbsite 423 K s hnh thnh cc vi tinh th boehmite, c
b mt ring t 200 ti 400 m
2
.g
1
.
X l nhit su hn na trong khong t 673 K v 1273 K thu c 1
lot cc tinh th chuyn tip ca aluminas nh sau: chi (), kappa (),
gamma ( ), eta (), theta (), v delta ().
Nhng oxit chuyn tip quan trng nht cho cc ng dng xc tc
l: -alumina v -alumina.
Khi nung trn 1273 K s thu c -alumina, l 1 vt liu khng
xp c cu trc tinh th.
OXIT N
Al
2
O
3
10
-Alumina v -alumina c gi l cc alumina hot ng. Nhng
vt liu ny t khi nm dng pha tinh khit, n c th cha cc trng
thi chuyn tip khc nm dng tp cht. Tnh cht ca chng ph
thuc rt nhiu vo loi nguyn liu ban u.
-Alumina th hin tnh axit Bronsted, Lewis, v tnh baz Lewis.
OXIT N
Al
2
O
3
11
OXIT N
Al
2
O
3
12
OXIT N
Al
2
O
3
13
OXIT N
Al
2
O
3
14
OXIT N
Al
2
O
3
15
-, - and -alumina thng c dng lm cht mang
-alumina: dng cho phn ng yu cu bmr thp. VD: oxy ho ring phn.
alumina c dng cho phn ng cn bmr ln, bn nhit v bn c
ng dng ni bt nht ca -alumina l cht mang cho thit b chuyn ho xc
tc cht nhim (alumina c ph bn ngoi vt liu monolith, sau cht
hot ng kim loi qu s c tm ln lp alumina ny).
Hoc ng dng khc cn bmr ln: cht mang xc tc trong cng ngh lc ho
du ( xng x l bng hydro). Alumina s mang cc cht hot ng xc tc
nh Co, Ni, v/hoc Mo.
Cc kim loi qu cng c mang trn alumina
-Alumina cng c th c dng nh 1 cht xc tc ring.VD: phn ng
hydrat (do n c tnh axit)
OXIT N
Al
2
O
3
16
OXIT N
Al
2
O
3
17
reactants
products
reactor
catalyst support
active site
substrate
adsorption
reaction
desorption
bed of
catalyst particles
porous carrier (catalyst
support)
product
OXIT N
18
im ng in PZC (Point of zero charge):
Gi tr pH m ti b mt trung ho in.
Nu pH > PZC b mt s mang in tch m
Nu pH < PZC b mt s mang in tch dng
OXIT N
19
Nu chng ta mun mang 1
anion ln trn cht mang
pH < PZC
Nu chng ta mun mang 1
cation ln trn mt cht mang
pH > PZC
PtCl
6
2-
D mang trn
alumina
OXIT N
20
Bc phn ng dng
Bc phn ng m
Trong nhng dng di y, dng no tt nht???
Ty thuc vo:
- ng hc phn ng
- Loi u c xc tc s din ra
Nu loi u c ming xp chim u th, cht xc tc t tin hoc qu trnh mi
mn nhiu, th nn pha hot ng nm pha trong tt hn
OXIT N
21
Highly dispersed metal on metal oxide
Nickel clusters
OXIT N
22
TiO
2
: xc tc axit yu
Bronsted: nhit thp
Lewis : nhit cao
Lc axit cao nht ca TiO
2
H
o
e -3, nhng axit kh nh
383 K: ch c dng anatase
573 773 K: hn hp ca dng anatase v rutile.
OXIT N
23
TiO
2
: cht mang rt tt cho cht hot ng xc tc
OXIT N
24
OXIT N
TiO
2
25
SiO
2
: xc tc axit yu
Si-OH: c tnh axit yu
OXIT N
26
OXIT N
SiO
2
27
Bin tnh SiO
2
Nha trao i
cation da
trn nn
sulfonate
styrene-
divinyl-benzen
Axit mnh c
ng dng nhiu
trong CN
Ko bn nhit
OXIT N
28
Silicagel tinh khit khng c hot tnh xc tc cho phn ng hydrat
isoproyl ru
Khi thm vo 0.1% ZrO
2
tnh axit v hot tnh xc tc tng ng k.
OXIT HN HP
Ti sao ???
Zeolite c tnh axit thay i theo t l Si/Al ???????????????????????
29
Nguyn tc Tanabe:
-S phi tr ca kim loi c gi nguyn
- S phi tr ca oxy ng vi oxit kim loi c thnh phn ch yu s c s
dng cho tnh ton s phi tr cho tt c cc oxy c trong hn hp
Chnh lch in tch, (z
(z = 0: oxit hn hp khng c tnh axit
(z < 0: oxit hn hp c tnh axit Bronsted
(z > 0: oxit hn hp c tnh axit Lewis
OXIT HN HP
30
CaF
2
NaBr
OXIT HN HP
31
T l bn knh s phi tr Kiu cu trc
r
+
/r
-
= 1 12 Cha c biet
0,732 < r
+
/r
-
< 1 8 CsCl
0,414 < r
+
/r
-
< 0.732 6 NaCl
0,225 < r
+
/r
-
< 0.414 4 ZnS
OXIT HN HP
32
OXIT HN HP
33
OXIT HN HP
34
OXIT HN HP
35
OXIT HN HP
36
OXIT HN HP
37
OXIT HN HP
38
OXIT HN HP
39
OXIT HN HP
40
Qu trnh sol gel cho php tng hp cc vt liu ceramic c tinh khit v ng nht cao.
Qu trnh ny xy ra trong dung dch ca cc tin cht hu c c kim (v d TMOS, TEOS,
Zr(IV) propoxide, Ti (IV) Butoxide, v.v). Cc phn thy phn v ngng t din ra s dn
n vic hnh thnh 1 pha mi (sol)
Sol c cu thnh t cc ht rn c ng knh t khong vi trm nm l
lng trong pha lng.
Cc ht rn ny sau s c ng li thnh 1 pha mi (gel).
Sy gel thu c nhit thp (25 -100
o
C) s thu c xerogel
c trng c bn ca phng php sol-gel l kh nng to vt liu ceramic
nhit gn nhit phng
OXIT HN HP
41
Cc phn ng trong qu trnh sol - gel
Thy phn
Ngng t
OXIT HN HP
42
Nguyn liu tt nht cho qu trnh sol gel l cc alkoxide kim loi
Cng thc chung: M(OR)n
M: kim loai
R: nhm alkyl
N: ha tr ca kim loi
Ngoi tr 2 cht c bit, tt c cc alkoxide cn li u thy phn rt nhanh
to thnh hydroxit hoc oxit tng ng
2 cht c bit: alkoxide ca silicon v photpho.
Silic alkoxide cn xc tc axit hoc baz cho phn ng thy phn, ngay c
lc c xc tc, phn ng ny vn chm.
OXIT HN HP
43
OXIT HN HP
44
1. To lp phim mng v cc lp ph
- Lp ph c tnh quang hc: v d: lm thay i
phn chiu, kh nng truyn qua, hoc c
kh nng chng phn x
- Lp ph c tnh cht in t: to cc lp ph c
kh nng dn in hoc c tnh siu dn
- Lp ph c tnh nng bo v hoc trang tr:
chng n mn, chng mi mn c hc
- To cc lp ph xp: ng dng trong lnh
vc membrane
2. Ch to cc si
3. Vt liu bt c kch thc nano
ng dng ca qu trnh sol-gel ng dng ca qu trnh sol-gel
OXIT HN HP
45
ng dng ca qu trnh sol-gel ng dng ca qu trnh sol-gel
OXIT HN HP
46
OXIT HN HP
47
Cc giai on trong 1 qu trnh tng hp
OXIT HN HP
48
OXIT HN HP
Oxit hn hp c tnh baz
1. TiO
2
MgO
2. Al
2
O
3
ZnO
3. Al
2
O
3
CaO
4. TiO
2
Al
2
O
3
5. TiO
2
ZrO
2
6. SiO
2
ZnO
49
OXIT HN HP
Bn knh kim loi thay th cng gn vi bn knh ca Mg
2+
th tnh baz cng
tng ( v kim loi d thay th cho Mg
2+
)
50
OXIT HN HP
Cc yu t nh hng n qu trnh to tm axit v baz
51
OXIT HN HP
To ra c tm axit ln tm baz (xem bng s liu)
52
OXIT HN HP
axit, lc axit v loi tm axit ph thuc vo qu trnh tng hp
53
OXIT HN HP
Gia nhit chuyn NH
4+
H
+
54
OXIT HN HP
1. C s hin din ca tm axit (xc nh bng cht ch th, o IR, hoc
c s lin h gia hot tnh xc tc vi s tm axit)
2. Hot tnh xc tc b u c bi cc baz hp ph
3. Xc tc cho cc phn ng c bit l theo c ch xc tc axit
55
OXIT HN HP
SiO
2
Al
2
O
3
Xc tc oxit hn hp c tnh axit tiu biu
Lc axit > H
o
= -8.2
C c tm axit Bronsted v Lewis
Axit Lewis tng khi tng nhit tin x l
Chuyn sang axit Bronsted khi hp ph nc
Phn ng tiu biu: polymer ho propen; isomer ho o-xylen;
cracking cumen
56
SiO
2
TiO
2
Tnh axit mnh
SiO
2
MoO
3
:
c tnh axit
SiO
2
ZnO
Va c tm axit va c tm baz
SiO
2
MgO
Va c tm axit va c tm baz
SiO
2
ZrO
2
C tnh axit mnh
OXIT HN HP
57
Al
2
O
3
- MgO
C c tm axit ln tm baz
OXIT HN HP
Al
2
O
3
- ZnO
C c tm axit ln tm baz
TiO
2
- MgO
C c tm axit ln tm baz