TOWARDS THE RATIONAL

TOWARDS THE RATIONAL

SYNTHESIS OF ZEOLITES
SYNTHESIS OF ZEOLITES
Roberto MILLINI
Roberto MILLINI
Physical Physical- -Chemistry Dept., EniTecnologie S.p.A. Chemistry Dept., EniTecnologie S.p.A.
Via F. Maritano 26, I Via F. Maritano 26, I- -20097 San Donato Milanese (MI 20097 San Donato Milanese (MI - - ITALY) ITALY)
e e- -mail: rmillini@enitecnologie.eni.it mail: rmillini@enitecnologie.eni.it
ZEOLITE: Microporous crystalline aluminosilicate with a framework
based on a 3D network of corner-sharing [TO
4
] (T = Si, Al) tetrahedra.
Depending on the structure, it contains channels and/or cages with
dimensions in the range 3 - 12 . The negative framework charge is
compensated by cations localized within the pores (extraframework
cations).
USES:
Molecular Sieve (e.g. separation of linear alkanes from branched ones)
Ion-exchange (e.g. water softening)
Catalysis (e.g. isomerization, alkylation, cracking,)
WHAT IS A ZEOLITE?
WHAT IS A ZEOLITE?
ZEOLITE STRUCTURES
ZEOLITE STRUCTURES
ESV
CHA
SMALL PORE
(8 MR)
MFI
FER
MEDIUM PORE
(10 MR)
LTL
MOR
LARGE PORE
(12 MR)
ZEOLITE SYNTHESIS
ZEOLITE SYNTHESIS
Silica source
Alumina source
Organic additive
Water
(alkali metal ions)
(sulphuric acid)
.
00:45
1 2 3 4 5
6 7 8 9 0
Separation
Drying
Calcination
Characterization
.
DESIGN OF SDA
MOLECULAR STRUCTURE
COMPUTER
COMPUTER
-
-
ASSISTED SYNTHESIS
ASSISTED SYNTHESIS
OF NEW ZEOLITES
OF NEW ZEOLITES
IDENTIFICATION
OF NEW (HYPOTHETICAL)
MICROPOROUS
FRAMEWORKS
SDA AND ZEOLITE
SYNTHESIS
No Well Established
Procedures Available
Computer Codes
Available
(e.g. ZEBEDDE;
D.W. Lewis et al., Nature
382 (1996) 604)
METHODS FOR GENERATING NEW
METHODS FOR GENERATING NEW
HYPOTHETICAL ZEOLITE FRAMEWORKS
HYPOTHETICAL ZEOLITE FRAMEWORKS
!Subdivide a known framework into layers that are then reconnected
after a crystallographic transformation (e.g. FAU/EMT, MFI/MEL,)
!Build new zeolite structures from molecular building units (Lego
chemistry; M.E. Davis CHEMTECH 24(9) (1994) 22)
!Simulated annealing (M.W. Deem and J.M. Newsam J . Am. Chem.
Soc. 114 (1992) 7189; M.B. Boisen Jr. et al., Microporous Mesoporous
Mat. 29 (1999) 219)
!Systematic enumeration of periodic 4-connected frameworks;
considering 1 unique T-atom, more than 6400 4-connected periodic
solutions were found and ~3% of these were refined to regular
tetrahedral topologies; when 2 unique T-atoms are considered, the
number of solutions is too high for being analyzed in reasonable time
(M.M.J. Treacy, K.H. Randall and S. Rao, Proc. 12
th
I ntern. Zeolite
Conf., Baltimore (MD), 1998, p. 517)
THE ROLE OF THE ORGANIC ADDITIVES
THE ROLE OF THE ORGANIC ADDITIVES
IN ZEOLITE SYNTHESIS
IN ZEOLITE SYNTHESIS
"VOID FILLERS
#GEL MODIFIERS
$TEMPLATES
%STRUCTURE DIRECTING AGENTS (SDAS)
New crystalline microporous compounds can be synthesized either by
using new SDAs with increasing complexity or by systematically
varying the synthesis parameters
TOWARDS NEW ZEOLITE STRUCTURES
TOWARDS NEW ZEOLITE STRUCTURES
NEW
NEW
ZEOLITES
ZEOLITES
NEW SDAS
SCREENING OF
SYNTHESIS PARAMETERS
OLD SDAS
N,N
N,N
-
-
DIMETHYLPIPERIDINIUM
DIMETHYLPIPERIDINIUM
ZSM-51 (NON)
US 4,568,654
ERS
ERS
-
-
7
7
LEV MOR MTW
(ANA)
?
THE SYNTHESIS OF ERS-7 (ESV) ZEOLITE
130C 155C 170C
3 days Amorphous ANA MOR
5 days Amorphous ANA ERS-7
7 days Amorphous ANA + ERS-7 ERS-7
14 days Amor. + ANA ERS-7 !!
Temperature and crystallization time (SiO
2
/Al
2
O
3
= 25)
SiO
2
/Al
2
O
3
molar ratio (temp. 170C, cryst. time > 5 days)
15 20 25 30 80 > 214
LEV ERS-7 + U ERS-7 ERS-7 + U MTW NON
R. Millini, G. Perego, L. Carluccio, G. Bellussi, D.E. Cox, B.J. Campbell, A. K. Cheetham, Proc.
12
th
Int. Zeolite Conf. (Baltimore, MD, 1998) 541
ZEOLITE STRUCTURE SOLUTION BY
ZEOLITE STRUCTURE SOLUTION BY
SIMULATED ANNEALING
SIMULATED ANNEALING
Simulated
annealing
optimization
- Addition of
O atoms
- Geometry
(DLS-76)
Validation
NO
YES
Refinement
- Unit cell size
- Space group
- Total T atoms
- Indep. T atoms
- (PXD, PND)
Deem & Newsam, JACS 114, 7189 (1992)
ERS
ERS
-
-
7 STRUCTURE SOLUTION
7 STRUCTURE SOLUTION
Primitive orthorhombic cell
a = 9.81, b = 12.50, c = 23.01
Space group: Pna2
1
or Pnma
No significant SHG signal suggests Pnma
INDEXATION (TREOR90)
5 10 15 20 25 30 35 40
" = 1.1528
Chemical composition:
Na
0.04
R
0.08
(Si
0.89
Al
0.11
)O
2
Total density: 2.04 gcm
-3
R + H
2
O = 15.5 wt% (TGA)
Na = 1.2 wt% (AA)
Density: 1.70 gcm
-3
Unit cell volume: 2821
3
48.1 T-sites/unit cell
6 to 12 independent T-sites
ERS
ERS
-
-
7 STRUCTURE SOLUTION
7 STRUCTURE SOLUTION
1000 simulated annealing cycles were run, with different random seeds,
assuming 6 independent T-sites
373 unique framework topologies were generated
The topology with the best zeolite figure-of-merit was found to be correct upon
comparing experimental and simulated XRD patterns
DLS-76
R = 0.000062
# = 0.000324
c
a
c
a
THE ERS
THE ERS
-
-
7 STRUCTURE
7 STRUCTURE
THE [4
6
5
4
6
5
8
2
] CAGE
THE [4
4
5
4
6
3
] CAGE
THE ROLE OF SDA MOLECULES
THE ROLE OF SDA MOLECULES
IN ZEOLITE SYNTHESIS
IN ZEOLITE SYNTHESIS
The zeolite which fits most closely around the SDA molecule will be
stabilized best by the SDA itself and, consequently, its formation will be
favored
Stabilizing effects of SDA are mainly due to the van der Waals
interactions while the chemical character of the organic molecule is not
very important [1,2]
An effective packing of SDA molecules is also fundamental for
stabilizing the overall system [2]
however:
depending on the synthesis conditions, a given SDA favors the formation
of different microporous frameworks, therefore, the relation SDA/zeolite
structure must be better understood
[1] H. Gies and B. Marler, Zeolites12 (1992) 42
[2] R. G. Bell et al., Stud. Surf. Sci. Catal. 84 (1994) 2075
THE DOCKING (PACKING) SCHEME
THE DOCKING (PACKING) SCHEME
ORGANIC MOLECULE
(SDA)
HIGH-TEMP. (e.g. 1500 K)
MOLECULAR DYNAMICS
ENERGY MINIMIZATION/
SIMULATED ANNEALING
MONTE CARLO DOCKING
(PACKING)
ZEOLITE FRAMEWORK
DOCKED (PACKED)
STRUCTURE
PACKING OF TPA IONS IN MFI
PACKING OF TPA IONS IN MFI
TEMPLATING ABILITY OF
TEMPLATING ABILITY OF
TETRAALKYLAMMONIUM CATIONS
TETRAALKYLAMMONIUM CATIONS
DOCKING ENERGY
MFI MEL *BEA
E
inter
(kJmol
-1
)
E
inter
(kJmol
-1
)
E
inter
(kJmol
-1
)
TMA -51.7 TMA -38.7 TMA -43.1
TEA -92.1 TEA -73.0 TEA -104.7
TPA -133.9 TPA -119.9 TPA -83.4
TBA -165.5 TBA -159.5 TBA -56.7
Experimental SDA in blue Predicted SDA in red
PACKING ENERGY
SDA/FRAMEWORK $E
pack
(kJmol
-1
)
TPA/MFI -29.7
TBA/MFI +14.9
TPA/MEL -8.5
TBA/MEL -18.3
[1] R. G. Bell et al., Stud. Surf. Sci. Catal. 84 (1994) 2075
TEMPLATE SELECTION USING DE NOVO
TEMPLATE SELECTION USING DE NOVO
MOLECULAR DESIGN METHODS
MOLECULAR DESIGN METHODS
To be effective as a templating agent, a molecule must effectively fill the
void cavity of the host framework
A cost function, f
c
, based on the overlap of van der Waals spheres
provides a suitable measure of the efficacy of a particular molecule for
the synthesis of a target framework
f
c
= %
t
C(tz)/n
C(tz) is the closest contact between a template atom t and any host atom
z; n is the number of atoms in the template
f
c
MUST BE THE MAXIMUM AT ANY TIME AND PROVIDES A
MEASURE OF TIGHTNESS OF FIT
D.J. Willock, D.W. Lewis, C.R.A. Catlow, G.J. Hutchings, J.M. Thomas, J . Mol.
Catal. A119 (1997) 415
ZEOLITES BY EVOLUTIONARY DE NOVO
ZEOLITES BY EVOLUTIONARY DE NOVO
DESIGN (ZEBEDDE)
DESIGN (ZEBEDDE)
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Actions: Build, Rotate, Shake, Rock, Random Bond Twist, Ring Formation, Energy
Minimization (Discover, MOPAC)
SDA VS. POROUS STRUCTURE
SDA VS. POROUS STRUCTURE
SDA shape Porous structure
Linear/cylindrical-shaped Monodimensional channels
Branched Intersecting channels
Spherical-like Cages
IN GENERAL, THE SDA DIMENSION AND SHAPE DETERMINE
THE SIZE AND THE SHAPE OF THE PORES
The presence of high concentration of trivalent metal ions (e.g. Al, B, Ga,
Fe, ) may influence the nature of the products
SYNTHESIS OF NEW ZEOLITES
SYNTHESIS OF NEW ZEOLITES
- COMPUTATIONAL-AIDED ROUTE
Design of SDAs through information coming from:
Evaluation of templating character of a given SDA in given
framework (modeling tools)
Investigation of SDA/framework interactions (experimental and
modeling tools)
- EXPERIMENTAL ROUTE
Trying new SDAs with more and more complex molecular structure
(limits: costs, availability,)
Exploring deeply the parameters involved in the zeolite synthesis
ASSESSING TEMPLATING PROPERTIES
ASSESSING TEMPLATING PROPERTIES
SDA
MOBILITY
13
C MAS NMR
SDA
LOCATION
MOLECULAR
DYNAMICS
NEW PROCEDURE
TEMPLATING
PROPERTIES
SDA/
UNIT CELL
BINDING
ENERGY
DOCKING
MINIMIZATION
TG ANALYSIS
OLD PROCEDURE
XRD
ZEOLITE SYNTHESIS IN THE PRESENCE OF
ZEOLITE SYNTHESIS IN THE PRESENCE OF
AZONIA
AZONIA
-
-
SPIRO COMPOUNDS
SPIRO COMPOUNDS
R. Millini et al., Microporous Mesoporous Mater. 24 (1998) 199
SiO
2
/Al
2
O
3
50 25
&
MOR (ERS-10)
MOR
MOR
MTW
ERS-10, MTW
MTW
[5,6]
[5,5]
[4,5]
MTW AND MOR STRUCTURES
MTW AND MOR STRUCTURES
MOR
[001]
MOR: [001] 12 6.5 x 7.0* '[010] 8 2.6 x 5.7* (17.2 T/1000
3
)
MTW
[010]
MTW: [010] 12 5.5 x 5.9* (19.4 T/1000
3
)
DOCKING AND PACKING CALCULATIONS
DOCKING AND PACKING CALCULATIONS
COMPUTATIONAL DETAILS
COMPUTATIONAL DETAILS
MODELS:
MOR: 113 SUPERCELL WITH 1 AND 5 SDA MOLECULES
MTW: 141 SUPERCELL WITH 1 AND 9 SDA MOLECULES
cff91_czeo FORCEFIELD
PERIODIC BOUNDARY CONDITIONS (PBC) APPLIED
PROGRAMS:
CATALYSIS 4.0.0 (MSI, 1996) (Models Building, Docking, Analysis)
DISCOVER 2.9.8 (MSI, 1996) (Energy Minimization, Molecular
Dynamics)
HARDWARE:
Silicon Graphics Indy
Silicon Graphics Octane
DOCKING AND PACKING CALCULATIONS
DOCKING AND PACKING CALCULATIONS
RESULTS
RESULTS
Binding energy, normalized to the number of non-H atoms (B.E.*) and
packing energy ($(
pack
) for the various zeolite/SDA combinations (data
in kJmol
-1
)
B.E.*
ZEOLITE SDA
Docking Packing
$E
pack
[4,5] -8.82 -13.91 -50.8
[5,5] -7.31 -13.34 -66.4 MOR
[5,6] -6.40 -12.09 -68.2
[4,5] -8.36 -12.36 -39.9
[5,5] -7.28 -9.70 -26.7 MTW
[5,6] -7.01 -7.16 -1.8
$E
pack
= E
1
- 1/nE
n
E
1
= Binding Energy of 1 SDA Molecule
E
n
= Binding Energy of n SDA Molecules
DOCKING AND PACKING CALCULATIONS
DOCKING AND PACKING CALCULATIONS
RESULTS
RESULTS
!B.E.* SLIGHTLY INCREASE AS THE DIMENSIONS OF THE SDA
INCREASE BOTH IN MOR AND IN MTW
!THE PACKING ENERGY CONTRIBUTES SIGNIFICANTLY TO
STABILIZE THE SYSTEM (WITH THE EXCEPTION OF SDA [5,6]
IN MTW)
!IN MOR THE PACKING ENERGY ($E
pack
) INCREASES IN THE
ORDER [4,5] < [5,5] < [5,6], WHILE IN MTW THE OPPOSITE
SITUATION IS OBSERVED
!TEMPLATING CHARACTER OF AZONIA-SPIRO COMPOUNDS
SEEMS TO BE HIGHER FOR MOR THAN FOR MTW
EVALUATION OF SDA MOBILITY
EVALUATION OF SDA MOBILITY
13 13
C MAS NMR SPECTROSCOPY
C MAS NMR SPECTROSCOPY
THE HIGHER THE SDA MOBILITY THE SHARPER THE NMR SIGNALS
MOR MTW
[5,6]
[5,5]
[4,5]
CONDITIONS FOR THE MD SIMULATIONS
CONDITIONS FOR THE MD SIMULATIONS
!NVT canonical ensemble, T = 300 K, time step = 0.5 fs
!ABM4 velocity integrator, Nos temperature control method
!Equilibrating step of 1 ps
!1000 ps (2500 ps for single SDA molecule) MD simulation with data
collection of coordinates and energy components every 1 ps
!Program used: Discover 2.9.8 (MSI, 1996)
EVALUATION OF SDA MOBILITY
EVALUATION OF SDA MOBILITY
MD SIMULATIONS
MD SIMULATIONS
0 500 1000 1500 2000 2500
time (ps)
0,0
0,2
0,4
0,6
0,8
1,0
M
S
D

(

*
*
2
)
N
RING 1
RING 2
Molecule
Ring 1
N atom
Ring 2
Diffusion tracks
EVALUATION OF SDA MOBILITY
EVALUATION OF SDA MOBILITY
MD SIMULATIONS
MD SIMULATIONS
Molecule
Ring 1
N atom
Ring 2
0 500 1000 1500 2000 2500
time (ps)
0
100
200
300
400
500
D
i
s
t
a
n
c
e

t
r
a
v
e
l
e
d

(

)
0 500 1000 1500 2000 2500
time (ps)
0,0
0,5
1,0
1,5
2,0
M
S
D

(

*
*
2
)
[4,5] IN MTW
0 500 1000 1500 2000 2500
time (ps)
0
5
10
15
20
25
30
M
S
D

(

*
*
2
)
0 500 1000 1500 2000 2500
time (ps)
0
100
200
300
400
500
D
i
s
t
a
n
c
e

t
r
a
v
e
l
e
d

(

)
[4,5] IN MOR
MD SIMULATIONS
MD SIMULATIONS
RESULTS
RESULTS
!NO TRUE MOLECULAR DIFFUSION PROCESS (D
~110
-11
m
2
s
-1
) SDA MOTION LOCALIZED AROUND
PREFERRED SITES
!THE SDA MOBILITY DECREASES IN THE ORDER:
[5,5]-MOR ) [4,5]-MOR > [5,6]-MOR > [5,5]-MTW ) [4,5]-MTW >
[5,6]-MTW, IN AGREEMENT WITH THE
13
C MAS NMR
DATA
!AZONIA-SPIRO COMPOUNDS DISPLAY HIGHER
TEMPLATING EFFECT FOR MTW THAN MOR
ARE THESE RESULTS USEFUL FOR
DESIGNING NEW SDAS?
OBSERVATION
SDA [5,5] FITS BETTER MWT THAN MOR
HYPOTHESIS
DIFFERENT ZEOLITE PHASES CAN BE OBTAINED IF WE
INCREASE THE STERIC HINDRANCE OF THE SDA AND WE
USE THE NEW SDAS IN THE SAME CONDITIONS WHICH
GIVE MTW (e.g. IN THE PURE SILICA SYSTEM)
MD SIMULATIONS
MD SIMULATIONS
RESULTS
RESULTS
*-Me-[5,5] *,*-di-Me-[5,5]
+,+-di-Me-[5,5] +-Me-[5,5]
+-Et-[5,5]
NEW
NEW
SDAS
SDAS
ZEOLITE SYNTHESIS WITH THE NEW
ZEOLITE SYNTHESIS WITH THE NEW
SDAS
SDAS
+,+-di-Me-[5,5] *-Me-[5,5] +-Me-[5,5]
MTW
MOR
*,*-di-Me-[5,5] +-Et-[5,5]
MEL
MEL
DOCKING CALCULATIONS
DOCKING CALCULATIONS
RESULTS
RESULTS
ZEOLITE VAN DER WAALS ENERGY (kJmol
-1
)
[5,5] +-Me-[5,5] +,+-di-Me-[5,5] *-Me-[5,5] *,*-di-Me-[5,5] +-Et-[5,5]
MEL -109.0 -119.4 -98.8 -121.3 -129.6 -132.2
MFI -87.0 -88.8 -83.6 -71.2 -89.6 -86.2
MOR -100.3 -104.9 -103.2 -103.9 -101.8 -98.3
MTW -103.6 -114.1 -104.4 -111.9 -105.1 -98.1
ZEOLITE RELATIVE VAN DER WAALS ENERGY (kJmol
-1
)
[5,5] +-Me-[5,5] +,+-di-Me-[5,5] *-Me-[5,5] *,*-di-Me-[5,5] +-Et-[5,5]
MEL 0 0 +5.6 0 0 0
MFI +22.0 +30.6 +20.8 +50.1 +40.0 +46.0
MOR +8.7 +14.5 +1.2 +17.4 +27.8 +33.9
MTW +5.4 +5.3 0 +9.4 +24.5 +34.1
&TBA favors the crystallization of MFI/MEL intergrowth with 75%
probability of i-type of stacking (MFI) and 25% probability of #-type
of stacking (MEL) [1]
&The first synthesis of defect-free MEL was reported in 1995, using
N,N-diethyl-3,5-dimethylpiperidinium (DDP) [2]
[1] G. Perego et al., J . Appl. Cryst. 17 (1984) 403
[2] Y. Nakagawa, WO Patent 95/09812
+-Et-[5,5] *,*-di-Me-[5,5]
SIMILAR
DDP
SYNTHESIS OF DEFECT
SYNTHESIS OF DEFECT
-
-
FREE MEL
FREE MEL
i
a
c
b
c
m
a
c
b
c
a
c
MFI
MEL
MFI/MEL
SBU
5-1
PerBU
THE PENTASIL FAMILY
THE PENTASIL FAMILY
Standard laboratory XRD
Sharp 110 reflection indicates
the lack of intergrowth
SXPD (GILDA -BM08, ESRF)
I4m2 space group
a = 20.0777(3), c = 13.4154(2)
Rwp = 0.0276, R(F
2
) = 0.0703,
Red. ,
2
= 1.213
R. Millini et al., 2
nd
FEZA Conf. (2002)
IS IT REALLY DEFECT
IS IT REALLY DEFECT
-
-
FREE MEL?
FREE MEL?
IS IT REALLY DEFECT
IS IT REALLY DEFECT
-
-
FREE MEL?
FREE MEL?
MEL/+-Et-[5,5]
E
vdW
= -132.2 kJmol
-1
MFI/+-Et-[5,5]
E
vdW
= -86.2 kJmol
-1
MEL/DDP
E
vdW
= -120.5 kJmol
-1
MFI/DDP
E
vdW
= -111.3 kJmol
-1
BASE SDA
STRUCTURE
MODIFICATION
Feasibility
Costs
Stability
.
DOCKING
MINIMIZATION
Compatibility With
The Porous Systems
Obtained With The
Parent SDA
SDA
SYNTHESIS
ZEOLITE
SYNTHESIS
DESIGN OF NEW
DESIGN OF NEW
SDAS
SDAS