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ISSN 2079-1704.
,
. 2014. . 5.
1. . 47-55
______________________________________________________________________________________________
544.72
.
,
.
,
.
Ti-MCM-41
.
, 13,
, 03164,
, E-mail: [email protected]
VOSO4
,
1.4
.%
,
Ti-MCM-41
.
,
,
,
0.3
. % V,
,
Ti-MCM-41
.
VOx
5 %V /V,Ti-MCM-41,
,
VOx
-41 Ti-
-41.
: MCM-41
,
,
,
,
,
,
[1, 7, 8],
M41S,
(
),
-
–
2
-41,
2.
Ti-
,
,
Ti
-41
,
[5].
[1].
2.5
1%
-41
(
[4]
,
Pt–Sn/Al2O3
Si/V = 30–50
)
Ti,V-
,
Oleflex [3].
©
.
.
,
.
, 2014
[9].
V,
[10],
Ti 2
-41
Ti [1, 5, 6]
-
V,
V
(
,
V
,
VOx/MCM-41
,
0.35
Ti
[6].
,
Ti,
) [2],
[3].
-41
. % Ti,
V
,
47
[7, 8].
-41
-41
-41
.
,
.
,
.
______________________________________________________________________________________________
VOx/MCM-41 [11].
[12],
-41,
Ti(
2
90 ° .
,
6
),
,
Ti,
Ti-
VxOy/MCM-41.
-41
V
VOSO4
V,Ti-MCM-41
-41, Ti-
-
Ti-41
: SiO2 : TiO2 : NaOH :
-Br : H2O = 1 : 0.019 : 0.2 : 0.2 : 30.
-41
V-41
,
-200 (
220 2 )
SiO2 : NaOH :
-Br :
H2O = 1 : 0.2 : 0.2 : 30
SiO2 : VOSO4 : NaOH :
-Br : H2O = 1 : 0.0024 : 0.34 : 0.5 : 30,
.
-
,
,
+
560 ° .
,
,
Na+
NH4Cl
-41
.
– VO(C5H7O2)2
,
.
V-Ti-
.
5
.
.
,
-41
1.4
TiO2
97.5
NaOH,
. % Ti (
. % SiO2)
. % VO
.
[12].
2
.%
(
)
-4-07
-Br) – C16H33(CH3)3NBr.
(
VOSO4 (5·10-3
NaOH
173
2.5
1
CuK
Ni
.
).
.
.
,
ASAP 2405 N Micromeritics,
VOSO4
623 K.
.
:
SiO2 : VOSO4 : TiO2 : NaOH :
1 : 0.024 : 0.019 : 0.34 : 0.5 : 30.
T (S
)
P/P0 = 0.05–0.3
-Br : H2O =
(V )
P/P0 = 0.95.
,
,
Ti
NLDFT (DDFT).
V
140 °
24 .
,
,
(
,
-
)
Elva 2.7.
110 °
.
6
560 ° .
48
ISSN 2079-1704.
2014. . 5.
1
Ti-MCM-41
______________________________________________________________________________________________
(
)
(
0.5–1.0 %)
–
(Carl Zeiss,
Jena,
Germany)
Specord M-40
.
–S
0.5
0.25–0.5 ,
4,
2
– SCO
– YC3H6.
2)
30
(
8,
– SC3H6,
2 4),
(
6,
,
0.3 ,
.1
.
7
.%
3
3
3.5
8
.%
2
He
7
.
,
.%
Ar.
8
(
2.5 .
300 °
25 °
2
30
)
. 1.
675 ° .
.
,
NaX,
,
.
-
V Ti
.2 , .
. 1.
– V,Ti-MCM-41. 1 –
(
,2–
,3–
: – MCM-41, – V-MCM-41, – Ti-MCM-41,
5 % VOx
. 1),
,
-
(hkl) – (100)
: (110), (200), (210),
ISSN 2079-1704.
2014. . 5.
.
,
1
MCM-41 [1].
MCM-41
,
[13].
49
,
,
.
,
.
,
.
______________________________________________________________________________________________
1000 ° ,
(
. 1).
,
.
.
1.
V Ti,%
TiO2
V
-41
H-41
5 %VOx/H-41
V-41
H-V-41
Ti-41
H-Ti-41
5 %VOx/H-Ti-41
Ti,V-41
H-Ti,V-41
5 %VOx/H-Ti,V-41
3.5
0
1.5
0
0
3.5
2.5
2.3
0.3
3.8
2.4
2.2
: V
0
SBET,
(100),
V ,
2
VDFT,
DDFT,
0.67
0.65
0.53
0.84
0.84
0.62
0.61
0.38
0.59
0.58
0.48
3.54
3.41
3.18
3.64
3.54
3.64
3.41
2.58
3.41
3.28
2.58
3
3
755
670
550
830
785
714
564
393
765
714
554
VDFT. DDFT –
: hW =
= 2 d100 3; (n = 2 d100 sin ).
-41
0.82
0.79
0.57
0.93
0.92
0.75
0.74
0.43
0.69
0.64
0.58
100,
2.35
2.3
2.25
2.15
2.15
2.15
2.1
2.15
2.1
2.05
2.1
0,
4.34
4.43
4.53
4.74
4.74
4.74
4.86
4.74
4.86
4.98
4.86
hW,
0.80
1.02
1.35
1.10
1.20
1.10
1.45
2.16
1.45
1.70
2.28
.
0
:
- DDFT
,
V-MCM-41
-41 (
,
. 1 , ),
VOSO4
[8, 14],
V [15].
[8],
. (1)
V
-
V5+
,
. (2)
2-
V
,
V-O (1.8 Å)
Si-O (1.6 Å),
. 1,
V-MCM-41
,
.
SBET, V , VDFT
DDFT
-41
(100)
. 2.
,
0
hW,
-41 [7, 8, 15].
50
:
– 1 – -MCM-41, 2 – -V-MCM-41, 3 –
5 % VOx/ H-MCM-41; – 1 - H-Ti-MCM-41;
2 – H-V,Ti-MCM-41; 3 – 5 % VOx/ H-TiMCM-41; 4 – 5 % VOx/ H-V,Ti-MCM-41
ISSN 2079-1704.
2014. . 5.
1
Ti-MCM-41
______________________________________________________________________________________________
215
,
Si/V = 40,
2
,
,
.
. % V.
[5, 6, 14],
Ti4+
(
. 1)
-V-MCM-41
-MCM-41 – 3.5
2-
,
. % V,
1.5
. % V,
(5 % V ).
V-MCM-41
V.
V
( .2 )
,
.
V, Ti-MCM-41
.1
VOSO4,
250–340
-41
hW,
-V,Ti-MCM-41
2
. % V,
,
0
.
,
V5+,
2-
.
(
. 1)
. % V.
~215
0.3
,
-V-MCM-41,
,
370
V5+
. 1,
-41
Ti-
,
250
-
Ti4+
,
V,Ti-MCM-41,
( .2 )
Ti-MCM-41
V5+
,
[8, 10, 14, 15].
V5+,
V5+
Ti.
Si4+ (0.41 Å),
(0.49 Å),
Si4+ Ti4+ (0.68 Å)
340 ,
[8, 10, 14, 15]
-
V5+
,
Ti
Ti-
2 [5, 6].
-41
.
,
Ti4+,
(100)
4+
Si [12],
.1 ,
(100)) Ti-41,
SBET
(
. 1).
.
,
V,Ti-MCM-41
,
-41
V,
,
Ti-MCM-41
,
.
[5],
Ti4+
Si
Si4+,
,
Ti
S+ I¯(
Ti
Si
),
SiO¯
4
Ti-
,
0
-41 (
Si–O–Si
,
,
[6].
Ti–O (1.9 Å)
hW Ti-41
. 1),
.
H-Ti-M
. 2 ),
SiO¯
i–O–V–O–Si,
Ti
-41
,
2014. . 5.
1
Ti–O–Si.
Ti-MCM-41
Si–O–V–O–Si
V5+
4+
Ti
.
ISSN 2079-1704.
,
-41,
51
.
,
.
,
.
______________________________________________________________________________________________
,
,
V,Ti-MCM-41
[10],
VO2+
,
,
.
5 % V x.
5 % VOx/H-V,Ti-MCM-41
.2 ,
5 % VOx/H-Ti-MCM-41
250 ,
V,
–
225 .
-
650–675 ° .
. 2.
2.
. 7 % 3 8, 3.5 % 2
He. = 2.5 .
SC3H6
XC3H8
YC3H6
56.6
10.4
5.9
53.3
23.4
12.5
61.1
14.9
9.1
55.4
23.1
12.8
78.1
38.4
30.0
77.4
41.7
32.3
75.6
43.7
33.0
75.2
46.0
34.6
60.6
34.9
21.1
53.0
40.7
21.6
77.9
57.6
44.9
77.1
61.0
47.0
63.0
37.6
23.7
60.5
41.5
25.1
80.7
60.5
48.8
78.7
63.8
50.2
,
HH-V-
650
675
650
675
650
675
650
675
650
675
650
675
650
675
650
675
-41
-41
5 % VOx/HH-Ti-
-41
-41
5 % VOx/H-TiH-V,Ti-
-41
-41
5 % VOx/H-V,Ti-
-41
SCOx
7.3
8.8
9.3
12.8
17.3
17.0
17.2
15.7
9.4
12.0
12.1
12.9
10.9
13.4
12.3
11.1
,
SC3H6
78.5
77.6
80.5
78.4
96.7
95.6
95.5
93.8
87.8
84.9
92.6
90.1
88.5
85.8
95.4
93.8
1.5
,
-
,
.7% 3 8
Ar. = 2.5 .
XC3H8
YC3H6
7.4
5.8
12.9
10.0
9.7
7.8
14.0
11.0
53.4
51.6
64.5
61.49
60.7
58.0
69.9
65.6
17.1
15.0
21.4
18.2
70.0
64.8
77.9
70.2
18.5
16.4
25.9
22.2
73.9
70.5
78.0
73.2
. % V,
,
5 %VOx/H.%
H-Ti-41
,
3.5
-41,
.
,
,
5 %VOx
[16].
. 2,
H-Ti-
,
.
-41
0.3 % V
,
650 °
5
,
.%
H-V,Ti-
VOx
-41
,
,
H-V-
-41,
(
).
-
,
.
52
ISSN 2079-1704.
2014. . 5.
1
Ti-MCM-41
______________________________________________________________________________________________
TiV-
VOSO4
-41
,
~ 1.5
-41
1.4
.%
. % V,
VO4
-41
,
-41,
-
,
,
,
-41,
V,
V,Ti.%
.
V
0.3
.
V-
Ti-
VOx
5 %VOx/H-
,
V.
-41,
-41
,
-41,
V-
VOSO4
,
Ti,
VOx
V-
-41 Ti-
,
-41.
Ti-MCM-41
.
.
,
.
, 13,
,
, 03164,
.
, [email protected]
VOSO4
,
1.4
.%
,
.
Ti-MCM-41
,
,
,
0.3
Ti-MCM-41
VOx
5 % V /V,Ti-MCM-41,
,
,
VOx
: MCM-41
,
. % V,
,
.
-41 Ti-
,
-41.
,
,
,
Synthesis of vanadium-containing Ti-MCM-41 silicates
and their catalytic properties in propane dehydrogenation
A.V. Redkina, N.D. Konovalova, K.N. Khomenko
Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
13 General Naumov Str., Kyiv, 03164, Ukraine, [email protected]
Ti-MCM-41 silicate with vanadium introduced in mesoporous structure has been obtained by
hydrothermal template synthesis with participation of VOSO4 and pyrogenic titanoaerosil with 1.4 wt. %
ISSN 2079-1704.
2014. . 5.
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53
.
,
.
,
.
______________________________________________________________________________________________
tetrahedrally coordinated titanium. By the X-ray diffraction, X-ray fluorescent spectroscopy, DR UV-vis
analysis and adsorption of nitrogen it has been shown that even 0.3 wt. % V causes raising spatial order
and hydrolytic stability of Ti-MCM-41. It has been found that additional supporting of VOx groups on a
surface of the synthesized bimetallic silicate allowed to obtain the catalyst 5 %VOx/V, Ti-MCM-41 which
due to dehydrogenation of propane generated propylene with bigger selectivity and yield than those when
VOx was supported on MCM-41 and Ti-MCM-41.
Keywords: MCM-41 mesoporous
dehydrogenation, propane, propylene
silicates,
hydrothermal
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S.A.,
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Tsilomelekis G. et al. Propane oxidative
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.,
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vanadium,
titanium,
structural stability, and nature of vanadium
sites in V-MCM-41? // J. Catal. – 2005. –
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.,
.,
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. II.
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//
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