Tutorial 6

- Zeolites and meso-porous materials

Jimmy Faria (Office ME 361)

Catalytic Processes and Materials
MESA+ Institute of Nanotechnology

01/10/2018 Meeting
Master Course 1
 Learning targets
§ Analyze the implications of the acidity and basicity of
zeolites on the catalyst performance

§ Analyze the interplay between meso-porosity and catalyst

performance

2
 Q1) Define acidity
Arrhenius definition
- Acid is a substance that increases the concentration of
hydronium ion (H3O+) when dissolved in water
- Base is a substance that increases concentration of
hydroxide ions (OH-)

Brønsted-Lowry definition
- Acid is a proton donor
- Base is a proton acceptor

Lewis definition
- Acid is an electron-pair acceptor
- Base is an electron-pair donor.
3
 Q1) Brønsted and Lewis Acidity
v Brønsted Acidity: Ability to donate a proton

v Lewis Acidity: Ability to accept an electron pair

What happens as
the temperature
increases? H2O removal

A) Phase separation + Brønsted Site

H
B) Dehydration O OH O O
C) Brønsted acid site is
transformed into a Si Al Si
Lewis acid site 4
+ + +
3 4
D) A+C O O O O

E) B+C

Brønsted and Lewis sites are interconvertible

 Q1) Brønsted and Lewis Acidity
v Brønsted Acidity: Ability to donate a proton

v Lewis Acidity: Ability to accept an electron pair

A Lewis acid
site is formed

Lewis Site O
O O

Si Al Si
+ + +
4 3 4
O O O O
 Q3) Ion Exchange Method
§ If we begin with NaY zeolite and we want to make the HY, we need to
exchange the Na+ by NH4+ and then calcine to eliminate NH3 and
leave H+ in the zeolite.

§ Calculate how many micromoles/g zeolite of acid sites can be

generated in a Y zeolite with a SiO2/Al2O3 ratio of 14 when the
exchange is 100 %

§ Atomic weights:
§ Na = 23
§ Si = 28
§ Al = 27
 Q3) Solution
Formula Dry basis Na Al Si7 O(14+2)

But, in the acid state: formula H Al Si7 O(14+2)

Element Moles M.W. Weight

H 1 1 1
Al 1 27 27
Si 7 28 196
O 16 16 256

Total Weight: 480 g cat

One H+ mole per 480 g cat
Then, Bronsted site density is : 2,083
micromoles/ g cat
 Q4) How to Measure the Acidity of Zeolites?
IR spectroscopy of adsorbed pyridine

N N
H+
O Al

Pyridinium Ion Coordinatively bonded

B
on a Bronsted site Pyridine to a Lewis site L

8
 Q4) Brønsted – Lewis Site Conversion

Explain the
observed trend
Brønsted sites
As the pretreatment
temperature
increases:

- first the density of

Lewis sites
Brønsted sites
increases (removal
of adsorbed water)

- then, Brønsted sites

begin to be
converted into Lewis
sites
of Heating before adding Pyridine
Volume adsorbed (cm3/g)

Relative pressure (P/Po)

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 Q5) Acid site strength
Isomorphous substitutions, either by direct synthesis or post-treatment, leading to
metallosilicates with zeolite structures where some of the T sites are replaced by a
trivalent element other than Al, such as Ga, Fe, In, B, etc., enables the tuning of the
acid strength of the catalyst. Both theoretical calculations and experimental acid
strength measurements by IR spectroscopy and ammonia TPD agree on the
following acidity ranking (48):

This order can be explained by a decreasing donor-acceptor interaction between

the oxygen atom of the silanol group and the trivalent element incorporated in the
structure and it has recently been obtained by density functional theory (DFT)
calculations by Bao (49).

11
 Q6) Acid Sites in Zeolites
Quantum
mechanical
calculations on
molecular
clusters

Note
difference with
acids in
solution …
every H3O+ is
the same H3O+

12
 Q7) TPD of alkyl amines
isopropylamine

(a) from weak acid sites, it desorbs the entire

molecule (m/e = 44)

(b) on strong Bronsted sites it decomposes into

* propylene (m/e = 41) and
* ammonia (m/e = 17)

C3H7 --NH2 ----> C3H6 + NH3

Ref.: Gorte et al.

* Appl. Catal. 67, 107 (1990)

* Appl. Catal. A90, 145 (1992)
* J. Catal. 129, 88 (1991)
* J. Catal. 148, 213 (1994)
 Q7) Characterization of Bronsted sites in HY zeolite
a) Sample A, almost all Al
ions in framework sites
each FA site makes one
Bronsted site. This leads
to strong acid sites that
can decompose
isopropylamine.

Sample B, a large fraction

of Al ions in extra-
framework positions
(alumina clusters). This
leads to weak acid sites
b) In the FCC process increasing the extra-framework that do not decompose
alumina species by steam pretreatment could lead to lower isopropylamine
acidity, which might reduce the cracking products. In
practice, however, this is often unavoidable as the steaming
process employed to cause dealumination and increase the
accessibility of the zeolites.
 Interesting fact:
What do you think that will happen in zero gravity?
Nothing…. Why?
Crystallization is
not affected by
gravitational
forces

NASA program:

a) Regular zeolite crystals

b) Zeolite Crystal grown under

microgravity in space.