Acidity

§ What is acidity ?
§ Can the acid strength be explained in
terms of structure and composition of
the solid ?
§ Is the acid strength related to catalytic
activity ?
§ How can it be measured ?

Catalysis by solid acids

OH groups silica (SiO2) But, when substituting

in
some Si4+ by Al3+
non-acidic STRONG ACIDITY
or weakly develops
acidic
H H H+

protonic acidity = Brønsted

 Brønsted and Lewis Acidity

v Brønsted Acidity: Ability to donate a proton

v Lewis Acidity: Ability to accept an electron pair

H2 O removal
Brønsted Site
H+
O OH O O

Si Al Si
+ + +
4 3 4
O O O O

Brønsted and Lewis sites are interconvertible

Brønsted and Lewis Acidity

v Brønsted Acidity: Ability to donate a proton

v Lewis Acidity: Ability to accept an electron pair

Lewis Site O O
O

Si Al Si
+ + +
4 3 4
O O O O
 Determination of B and L sites by IR spectroscopy
of adsorbed pyridine

N N
H+
O Al

Pyridinium Ion Coordinatively bonded

on a Brønsted site Pyridine to a Lewis site

Brønsted – Lewis Site Conversion

As the pretreatment
temperature
increases: Brønsted sites

- first the density of

Brønsted sites
increases (removal
of adsorbed water) Lewis sites

- then, Brønsted sites

begin to be
converted into Lewis
sites
 In most cases, the important value
is the Brønsted Site Density

Correlation of
Brønsted Site
Density with
Activity

Correlation of Brønsted Site Density with Activity

Example: Cumene cracking
 Acidity and Acidity Strength

The term “Acidity” implies:

a) an extensive property:
density of acid sites on the catalyst surface
(moles/g cat.) Sometimes it is called Acid Density.
b) an intensive property:
ability to protonate bases of different strengths
This property is called Acidity Strength

Determined by structure, coordination, and partial

charge on the surface. Enthalpy change of
neutralization of a base.

Acid Solutions and Solid Acids

§ Acid Solutions contain only one type of acid:

H3O+
§ only the extensive factor of acidity is measured

§ On solid surfaces:
o Every OH group, potentially a Brønsted site
o Therefore, distribution of site strengths
 Acidity measurement
1. TPD of adsorbed ammonia
Strong Sites
CAUTION:
textural effects
area is proportional may

Desorbed ammonia
to the density of sites modify the position
and
relative intensities

position is a Weak
function of strength Sites
of the acid sites

Temperature

Acidity measurement
2. TPD of alkyl amines
isopropylamine

(a) from weak acid sites, it desorbs the

entire
molecule (m/e = 44)

(b) on strong Brønsted 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)
 Characterization of Brø
Brønsted sites in HY zeolite
§ sample A, almost all Al ions in framework sites each FA site makes
one Brønsted site

§ sample B, a large fraction of Al ions in extra-framework positions

(alumina clusters)

Acidity
measurement
3.-
3.- Microcalorimetry

from area
heat can be determined
 Microcalorimetry
Heat of adsorption of pyridine on H-Mordenite as a
function of pyridine coverage

Heat of adsorption of Pyridine

260
240
220
200
kJ/mol

180
160
140

120
100
0 200 400 600 800

Adsorbed Pyridine (micromoles/g)

TPD of pyridine adsorbed on H-

H-Mordenite

Desorption rate Adsorption conducted

3.0
at 200oC on a
volumetric system.
2.5
Pressure range 0-5
micromol/g K

2.0 Torr.
Sample pre-treated in
1.5 oxygen (4 h) and
then under
1.0 evacuated 10-7 Torr
(1 h) at 400oC
0.5 Dumesic et al. (1993)
0.0
400 600 800 1000 1200

Temperature (K)
 E(θ)
Using the Elovich Equation for TPD and the E(θ
obtained by microcalorimetry, fit the TPD curve
Elovich Equation
dθΑ /dT = - (ko/β) θΑn e–E/RT

2.5
Desorption rate

1.5

0.5

0
450 600 750 900 1050

Temperature (K)

Differential heat of adsorption of ammonia on a solid acid

SILICA-ALUMINA CATALYSTS
§ A) 30% alumina

§ B) 13% alumina

§ C) 1% alumina

§ D) same as B but
pretreated with ammonia

§ E) 0% alumina

The number of strong acid sites (heat of

adsorption higher than 80-90 kJ/mol)
increases by the addition of Al3+ due
to generation of Brønsted sites.

NOTE: Number of strong acid sites

Ref. K. Tanabe et al. “New Solid Acids is much lower than the number of
and Bases” Elsevier Vol. 51
(1989) p.10 Al ions. Why ?
Effect of Si/Al Ratio and Geometry
§ The acidity strengths of the most
common acidic zeolites follows the
order:
H-Mor > H-ZSM-5 > H-Y

§ Can this trend be rationalized in

terms of structure and composition
(Si/Al ratio) of the zeolite ?

The Si/Al ratio changes the number of

neighboring Al atoms around the bridging
Hydroxyl group

O O O
O Si Al O
O O

Lowenstein rule: Two negatively charged Al ions

can never occupy neighboring positionsc
 Si H Si Al H Si
O O O O O O
Si O Si Al O Si Si O Si Al O Si
O O O O
Si Si Si Si
High Si-zeolite (H-ZSM5) Si/Al ratio = 7 Typical H-Y zeolite. Si/Al ratio = 3

Al H Si Al H Si
O O O O O O
Al O Si Al O Si Al O Si Al O Si
O O O O
Si Si Al Si
Some H-X zeolites. Si/Al ratio = 1.7 Si/Al ratio = 1

Calculated Positive Charge and Proton Donor

ability of the OH groups
Ref. V. B. Kazansky “Structure and reactivity of Modified Zeolites”
Elsevier (1984) p. 61

Si/Al ratio q(+) in H proton abstraction energy

7 0.404 14.96 eV
3 0.392 15.32 eV
1.7 0.384 15.60 eV
1 0.376 15.89 eV
SiOH 0.317 17.00 eV

Conclusion: The acidity strength increases with

the Si/Al ratio.
Polarizing effect of the negatively charged Al center
neutralizes the positive charge on the bridging OH.
 Al H Si
O O O
Si O Si Al O Si
O O
Si Si

Effect of bond angle in zeolite acidity

Calculated potential energies for several T-O-T bond angles
(Carson et al.)
POTENTIAL ENERGY

H+
O
Deprotonated form

easy to lose
Al Si
hard to lose

Protonated form

Al-O-Si Bond Angle

Protonated form becomes less stable from 130 to 175o. As a

result, the energy required to deprotonize bonds decreases at
large
T-O-T angles. ACIDITY INCREASES
 Some zeolite T-
T-O-T bond angles

q HY zeolite (moderately strong acid)

angles: 138, 139, 145, 147o

q H-ZSM5 zeolite (strong acid)

26 different bond angles ranging from 137 to
177o
Preferential Al sites (145 to 168o)

q H-Mordenite (very strong acid)

angles: 143 to 180o

Acid-
Acid-Catalyzed Reactions
q Double-Bond Isomerization
q Skeletal Isomerization
q Cracking
q Oligomerization

Elementary Steps
q Hydride Shift
q β-scission
q Methyl shift (via 3C- ring)
q Carbenium ion addition
q Hydrogen Transfer
 Activation of Hydrocarbons

A double bond in an olefin can be attacked

by a proton (Brønsted site) , forming a
carbocation (carbenium ion)

A hydride can be abstracted from a parafin by

a Lewis site (carbenium ion)

A very strong acid site could protonate a

parafin, forming a penta-coordinated
carbocation (carbonium ion)

Formation of a carbenium ion

Protonation of an olefin by a Brønsted site

hydride abstraction from a parafin by a Lewis site

The carbonium ions are unstable and can quickly
turn into carbenium ions, starting the carbenium
ion chemistry described above.

Example: C2H6 + H+ → C2H7+

C2H7+ → C2H5+ + H2

Relative stabilities of carbenium ions

tertiary carbenium ion is more stable than secondary
and secondary more stable than primary
 Double-
Double-bond isomerization
of 1-
1-butene (hydride shift)
§ proton attack to the double bond on Bronsted site:
H2C=CH-CH2-CH3 + H+ ----> H3C-CH-CH2-CH3
+
sec-butyl cation
§ internal hydride shift:
H3C-CH-CH2-CH3 ----> H3C-CH2-CH-CH3
+ +
§ proton elimination:
H3C-CH2-CH-CH3 ----> H3C-CH=CH-CH3 + H+
+

Cracking (β-
(β-scission)
§ Secondary carbenium ion formation (at
random)
§ Scission of bond β to carbon with positive
charge, giving an α-olefin and a primary
carbenium ion
• Cracking of straight-chain secondary carbenium intermediate
occurs at the bond located β to the carbon atom bearing the
positive charge (TWO ELECTRONS GO TO R)

RCH 2 C HCH 2 − CH 2 CH 2 R ′ ← → RCH 2 CH = CH 2 + C H 2 CH 2 R ′

+ +

• Primary carbenium generally undergoes rapid hydride shift to

form more stable secondary ion:

C H2 CH 2 R ← → CH 3 C HR
+ +
 No ethylene formed in catalytic
cracking

C2, C1 species are typically not observed in catalytic

cracking in contrast to thermal cracking

+ +

β Scission β Scission not

possible

and this one is not

stable +

Most Important Characteristic of

Zeolites in Cracking:
Hydrogen Transfer
Fate of carbenium ion on surface:
- continue β-scission until cannot longer crack
- pick-up a hydride and desorb as a parafin
(chain transfer):

If this transfer is efficient:

SHORTER TIME ON SURFACE

LESS GAS LESS COKE MORE GASOLINE

 Hydrogen Transfer in Zeolites

§ Few olefins are observed over zeolite catalysts

due to rapid hydrogen transfer
ü from cycloparaffins and cycloolefins, producing
paraffins + aromatics
ü from other olefins, producing paraffins + cycloolefins
or aromatics

§ The improved hydrogen transfer on zeolite

catalysts (versus silica-alumina alone or other
solid catalysts) results in markedly increased
conversion to gasoline-range hydrocarbons by
preventing further cracking.

Improved Product Distribution of

Zeolites

Note enhanced distribution

of products in the gasoline
range
 Coke Formation
l Coke forms via aromatic intermediates.
l Even in the absence of aromatics in the feed,
coking will occur following cyclization.

Coke Formation From Various Pure

Hydrocarbons
l Which of these compounds will give the fastest
formation of coke ? Rank them in order of coke
formation ability

1 3
naphtalene decalin

4 3,3 dimethyl-1-octene
2
tetralin 5 Decane

2-ring aromatics > 1-ring aromatics > olefins >

paraffins
 Other Observations on Coke Formation
§ Rate of coke formation increases with base strength of
hydrocarbon (i.e., ease of carbenium ion formation).

§ Rate of coke formation increases with acid strength of

catalyst.

§ Rate of coke formation increases with acid site density

(suggesting dual or multiple site reaction mechanism).

§ Coke combustion is a significant source of energy to

drive the endothermic cracking reactions.

§ Hydrogen from coke formation is a significant source

of hydrogen terminating cracking reactions.

Reactor Design and Operation

Three-component model (gas oil, gasoline and

diesel, and coke and other gases) model of
Weekman and Nace (Nace et al., Ind. Eng. Chem.
Process Des. Dev., 10, p. 530, 1971)

From this analysis one can determine the optimum conversion

Prediction of Gasoline Yield Vs.
Conversion
At moderate conversions, the
gasoline yield has a
maximum.

Coke and Gases increase

continuously.

LCO (light cut oil) has a

maximum, while HCO
(heavy cut oil) decreases
continuously
To maximize gasoline yield
it’s necessary to work at
intermediate conversions

Isomerization of Alkanes
Carbonium ion formation
and methyl shift (3C ring)
 n-pentane isomerization on acid
catalysts
C H+
C C C C C C C C C
+ regardless of
where the ring
opens
C C
H-- transfer
C C C C C C C C
+ +

n-C5H12

i-C5H12 + C5H12+

Hydride abstraction

n-butane isomerization on acid

catalysts
2
C 3 H+
C C C C C C C
1
+

§ if bonds 1 or 2 break C C C C
+
secondary carbenium ion does not
lead to isomerization
C
§ if bond 3 breaks
C C C
+
isobutyl cation could lead to isomerization
after hydride transfer. However, primary carbenium
ion results in a very high activation energy and
much lower rates than for n-pentane isomerization.
 Activation energy for the isomerization
of n-
n-butane
C

C C C
+

C H+
18 kcal/mol
C C C

3 kcal/mol
C C C C
13 kcal/mol
+

C C C
+