钛硅分子筛的研究进展

Limtrakul. J.,et al., J. Mol. Catal., 207 (2004) 137
Surroundings of Ti
OSi SiO Ti OSi OSi
OH
Si O
O
Ti O
OH Si
Mechanism 1 of TS-1
OSi SiO Ti OSi OSi H2O2 Si O Si O O Si Ti OOH HO Si Si O Si O H2O2 O Si Ti O C Si O Si O Ti OH HO Si O C C Si O Si O R O H O C HO Si H ROH (R=H, Me, Et)
Outline
Background and application of
the Titanosilicate Preparation and characterization of the Tianosilicate Structure and mechanism of the Tianosilicate
Keshavaraja. A.,et al.,J. Catal. 157 (1995) 501
Application of TS-1
OH OH OH
+
Already Industrialized (10,000t/a)
OH OH
OH
RR’CHOH
promising industrialized
TS-1 + 30 %H2O2
Later , the preparation of Ti-ZSM-11, Ti-MCM-41 Ti-
HMS and Ti-MSU were reported.
Speciality of TS-1
Reacted under mild condition
(0℃-100℃, air pressure)
R
O H O HO Si H C
— ROH
Ti
O C
O Si
O Si
Notari. B., Adv. Catal. 41 (1996) 253
Mechanism 2 of TS-1
O
Ti H2O2
OH Ti
XRD of TS-1
The evident of the orthorhombic structure of TS-1
Bengoa. J. F.,et al., Micropor Mesopor Mater 24 (1998) 163
The Structure of MFI
Structure of TS-1
R R O
RR’CH2
By-product: only water !!!
RR’CHOH
O + NH3 NOH
R O R’
Already Industrialized （12,000t/a)
The route of pBiblioteka Baidueparing TS -1
Gas-solid isomorphous replacement
混合液 Template:
TPA+ TBP+/TEP+ TBA+/TEA+ TPA+/TEA+
Crystallized, filtrated,
washed, dried, calcined
TS-1
Mineralising agent:
OH- NH4+ Methylamine Hexanedimine
method
In-Situ embedded method
Hydrothermal method
Hydrothermal method
Si Source:
TEOS Fumed silica Colloidal silica Amorphous SiO2
Ti Source:
TEOT TPOT TBOT TiCl3 TiCl4 Amorphous TiO2
Background of TS-1
In1967，the zeolite containing TiⅣ was mentioned in US
3329480
In1983， the preparation and characterization of TS-1
was reported by Taramasso (Italy) in US 4410501
Cundy. C. S., et al., Chem. Rev., 103 (2003) 663
SEM of TS-1
Wilkenhoner.U., et al., J. Catal. 203 (2001) 201
IR spectra of TS-1
Pirutko.L. V., et al., Micropor Mesopor Mater 48 (1998) 345
Mechanism of structure direction and crystal growth in the synthesis of TS-1
Si
O O
O N+ OH
O Si O
Solution of Ti and Si
N+
OH
Ti O O
growing
growing
The growing of template simulated by computer
Notari. B., Adv. Catal. 41 (1996) 253
The advent of TS-1 represented the next major innovation enabling shape-selective oxidations to be carried out in industrial scale
Remarkable shape-selectivity Friendly
The pore of TS-1 is about 0.5nm
Evaluation of TS-1
The selective oxidation of organic substrates by H2O2 in the presence of TS-1 is an interesting area of high potentiality for development of new environmentally friendly technologies