Mesoporous Zeolites : Synthesis and

Characterization

By: Rajdeep Doley

(140107047)
Under the guidance of: Dr. Nageswara Rao Peela
Department of Chemical Engineering
Indian Institute of Technology, Guwahati
Objectives of the experiment:

 Synthesis of the mesoporous zeolites.

 Studying the effects of hydrothermal time, Sodium- Aluminum ratios,
uses of templates, etc on the production of the zeolites.
 Perform various tests on the produced zeolites and characterize them
accordingly.
Steps of preparation of the zeolite:

 DDW is taken in a Teflon autoclave and stirred continuously.

 NaOH is added to the DDW in the autoclave and kept stirring.
 SiO2 is slowly added to the aqueous solution to get proper and even mixing.
 After that, NaAlO2 is slowly added to the gel like mixture while continuously
stirring it so as to have an even mixture.
 Finally, the seeds are added, stirred and heated at 180ºC for the required
amount of hydrothermal time.
 The Teflon autoclave is cooled after the required amount of time and dried to
get the required product.
XRD analysis : XRD or X-Ray Diffusion analysis helps to know
about the phase of a particular substance. It also helps to give
information about the d spacing, the spacing between two molecules of a
particular compound and also the crystallinity of the particular
compound which then the compound can be used accordingly in many
industries such as the petrochemical industry.
BET analysis:
Brunauer-Emmett-Teller (BET) theory aims to explain the physical adsorption of
gas molecules on a solid surface and serves as the basis for an important analysis
technique for the measurement of the specific surface area of the materials. It also
tells us about the porosity, the amount of pores in a particular area etc. The BET
theory normally uses probing gases that do not chemically react with material
surfaces as adsorbents to quantify specific surface area.
Results and Discussions:
Preparation on ZSM-5 by varying the reaction time (60 SiO2:Al2O3:7.2
Na2O:1500 H2O)
Reactant used Mass of it used (in grams)
H2O 22.4663
NaOH 0.3956
SiO2 3
NaAlO2 0.1543
Seeds 0.05
Reaction Conditions:
 For the 24 hours reaction, weight of the compound gained is 2.675 g. Yield: 89.167%
 For the 48 hours reaction, weight of the compound gained is 2.3141 g. Yield: 77.136%
 For the 12 hours reaction, weight of the compound gained is 2.1628 g. Yield: 72.09%
 For the 18 hours reaction, weight of the compound gained is 2.2829 g. Yield: 76.096%
Preparation of ZSM-5 by varying the SAR’s:
1. For Sodium-Aluminum ratio-30(30 SiO2:Al2O3:3.6 Na2O:750 H2O)

Reactants used Mass of it used (in grams)

H2O 22.4663
NaOH 0.3956
SiO2 3
NaAlO2 0.1543
Seeds 0.05
Reaction conditions:

 Temperature: 180ºC
 Reaction time: 18 hours
 Weight: 2.5786 g
 Yield: 85.953%
2. For Sodium-Aluminum ratio 90 (90 SiO2:Al2O3:10.8 Na2O:2250 H2O)

Reactants used Mass of it used (in grams)

H2O 22.4663
NaOH 0.3956
SiO2 3
NaAlO2 0.1028
Seeds 0.05

Reaction conditions:

 Temperature: 180ºC
 Reaction time: 18 hours
 Weight: 2.2136 g
 Yield: 73.786%
3. For Sodium-Aluminum ratio 120 (120 SiO2:Al2O3:14.4 Na2O:3000
H2O)

Reactants used Mass of it used (in grams)

H2O 22.4663
NaOH 0.4411
SiO2 3
NaAlO2 0.0771
Seeds 0.05

Reaction conditions:

 Temperature: 180ºC
 Reaction time: 18 hours
 Weight: 2.0419 g
 Yield: 68.063%
XRD analysis graphs:

 At lower hydrothermal time, amorphous

peak was observed at around 20-25 θ.
 The impurity at 48 hours is due to quartz
formation.
 At 18 hours and 24 hours, the zeolite is
perfectly crystalline.

Fig 1: XRD analysis graphs for varying hydrothermal times.

  At higher SAR’s the zeolite
displays amorphous
characteristics.
 Zeolites at lower SAR’s display
crystalline properties.

Fig 2: XRD analysis graphs for different SAR’s

BET analysis:
Sl Catalyst S BET a S BJH b (m2/g) S t-plot c P D d (nm) V TPV e V t-plot f V BJH g
No (m2/g) (m2/g) (cm3/g) (cm3/g) (cm3/g)

1 ZSM-5 (30) 274.72 33.08 203.07 2.50 0.172 0.031 0.041

2 ZSM-5 (90) 82.55 18.72 41.45 8.11 0.167 0.021 0.102
3 ZSM-5 (120) 98.57 17.72 58.14 7.61 0.188 0.030 0.159
4 ZSM-5 (18 hr) 238.60 12.17 194.25 2.42 0.144 0.100 0.022
5 ZSM-5 (12 hr) 147.20 56.79 108.97 3.97 0.146 0.056 0.041
6 ZSM-5 (24 hr) 300.04 14.70 228.23 2.61 0.196 0.118 0.037

Glossary:

S BET a - BET surface area (0.05-0.3 P/Po) S BJH b - BJH Surface area (0.35-0.99 P/Po)
S t-plot c- t-plot micro pore surface area (0.08-0.3 P/Po) P D d - Avg Pore diameter
V TPV e- total pore volume (0.99 P/Po) V t-plot f- t-plot volume (0.08-0.3 P/Po)
V BJH g- BJH volume (0.35-0.99 P/Po)
 ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O) at 180°C and
hydrothermal time 18 hrs.
120
Quantity Adsorbed (cm3/g STP)

100

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 3: BET analysis of ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O)

synthesized at 180°C and hydrothermal time 18 hrs.
 ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O) at 180°C and
hydrothermal time 12 hrs.
120

100
Quantity Adsorbed (cm3/g STP)

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 4: BET analysis of ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O)

synthesized at 180°C and hydrothermal time 12 hrs.
 ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O) at 180°C and hydrothermal
time 24 hrs.

140

120
Quantity Adsorbed (cm3/g STP)

100

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 5: BET analysis of ZSM-5 (60 SiO2:Al2O3:7.2 Na2O:1500 H2O)

synthesized at 180°C and hydrothermal time 24 hrs.
 ZSM-5 (30 SiO2:Al2O3:3.6 Na2O:1500 H2O) at 180°C and
hydrothermal time 18 hrs.
120

100
Quantity Adsorbed (cm3/g STP)

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 6: BET analysis of ZSM-5 (30 SiO2:Al2O3:3.6 Na2O:1500 H2O)

synthesized at 180°C and hydrothermal time 18 hrs.
 ZSM-5 (90 SiO2:Al2O3:10.8 Na2O:2250 H2O) at 180°C and
hydrothermal time 18 hrs.
120

100
Quantity Adsorbed (cm3/g STP)

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 7: BET analysis of ZSM-5 (90 SiO2:Al2O3:10.8 Na2O:2250 H2O)

synthesized at 180°C and hydrothermal time 18 hrs.
 ZSM-5 (120 SiO2:Al2O3:14.4 Na2O:3000 H2O) synthesized at 180°C
and hydrothermal time 18 hrs.
140

120
Quantity Adsorbed (cm3/g STP

100

80

60

40

20

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative pressure (P/Po)

Fig 8: BET analysis of ZSM-5 (120 SiO2:Al2O3:14.4 Na2O:3000 H2O)

synthesized at 180°C and hydrothermal time 18 hrs.
Conclusions:
 The ZSM-5 zeolite was successfully synthesized by using seeds as an agent and by
using the hydrothermal method.
 The XRD analysis was done and showing that all the zeolites that were synthesized
were crystalline in nature.
 During the process of the experimentation, ZSM-5 synthesis was studied at different
hydrothermal times and it was found that at lower hydrothermal times, the zeolites were
amorphous in nature and at higher hydrothermal times, it tend to have improper peaks.
 The effect of SAR’s were also studied and it was found that at lower SAR’s, the
zeolites were easily crystallized and can form pure zeolite phases.
 The BET analysis reveals that most of the synthesized materials contains micro pores.
 Finally, in the end it can be concluded that the optimized reaction conditions for the
production of the zeolites according to the experiment is at SAR-60, 180°C and 18hr
and is found to be best for fast and pure crystallite zeolite synthesis.
Thank you!