Outline
Background and application of
the Titanosilicate Preparation and characterization of the Tianosilicate Structure and mechanism of the Tianosilicate
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
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 preparing TS -1
Gas-solid isomorphous replacement
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
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
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
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
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
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
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 OБайду номын сангаасSi 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)
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)
混合液 Template:
TPA+ TBP+/TEP+ TBA+/TEA+ TPA+/TEA+
Crystallized, filtrated,
washed, dried, calcined
TS-1
Mineralising agent:
OH- NH4+ Methylamine Hexanedimine