Zeolitic Materials: Ion Exchange and Shape Selective Catalysis

Angus P. Wilkinson School of Chemistry and Biochemistry Georgia Institute of Technology Atlanta, GA 30332-0400

Overview
Introduction Zeolite structure Zeolite synthesis Zeolite application

What is a zeolitic material?

Zeolites are inorganic crystalline solids with small pores (1-20 diameter) running throughout the solid They are aluminosilicate framework structures made from corner sharing SiO4 and AlO4 tetrahedra
related structures can be made from AlPO4 and other compositions

Building up zeolite structures

Secondary building units

Pentasil zeolites

Pore connectivity

Chiral zeolites
A chiral zeolite would allow enantioselective synthesis and separations
Very difficult to get optically pure chiral zeolite

What is special about zeolites?

They have pores with molecular dimensions
leads to shape selectivity

There is a narrow range of pores sizes in the solid because the materials are crystalline
gives better selectivity than non-crystalline materials

Pore sizes in zeolites

Zeolite A, ZSM-5 and Beta

Zeolite Beta 12 rings

Zeolite A 8 rings

ZSM-5, 10 rings

What types of applications are zeolites used for?

Drying agents
used for drying solvents

Shape selective separations

e.g. dewaxing diesel fuel

Shape selective catalysis

predominantly acid catalysis, but also redox

Selective ion exchangers

water softeners, radioactive waste treatment

Shape selectivity

Key structural features

You can make materials with a wide range of pores sizes and shapes Composition can be varied to tailor a materials properties
pure SiO2 zeolites tend to be hydrophobic high alumina zeolites have a lot of charge balancing extraframework cations and have a very high affinity for polar molecules

Extraframework cations
Extraframework cations are under-coordinated by the framework
like to bind molecules in pore system to increase coordination number

Extraframework cations in Faujasites

Undercoordinated cations

3A, 4A, 5A etc.

What are 3A, 4A, 5A and 13X?
The number denotes the accessible pore size the letter denotes the framework changing cations tunes the pore size

ALPOs
Microporous aluminophosphates can also be made Synthesis is usually at low pH with organic additives ALPOs have no framework charge SAPOs have a negative charge on the framework ALPOs limited to ring systems with alternating aluminum and phosphorous

Titanosilicates
It is possible to make Zeolite frameworks that include tetrahedral titanium A class of materials containing octahedral titanium has also been prepared These titanosilicates are useful catalysts for selective partial oxidation reactions using peroxide oxidizing agents

Zeolite synthesis
Zeolites and aluminophosphate microporous materials are made hydrothermally
reactants are heated in water (100 - 250 C) For an aluminosilicate zeolite
silica source: Cabosil, sodium silicate or Si(OEt)4 alumina source: high surface area aluminum oxyhydroxide, Al(OEt)3, sodium aluminate, Al3+ salts base (pH ~12); alkali metal hydroxide, quaternary ammonium hydroxide etc. template: organic cation, hydrated metal ion etc.

Templating agents
Pore size and shape can be controlled by growing the zeolite around templates

TMA+ in ZK-4

TPA+ in ZSM-5

Typical zeolite products

Usually, zeolites are polycrystalline

Characterization
Most zeolite do not grow into large single crystals Structural data can be obtained from:
i) powder diffraction techniques ii) electron microscopy iii) solid state NMR spectroscopy

Zeolites and powder diffraction

Electron microscopy and zeolites

29Si

MAS NMR of zeolites

Ion exchange with Na-A

More sodium zeolite A is produced than any other zeolite It is used as a water softener in powdered laundry detergents In countries with low waste water treatment standards it is more environmentally friendly than polyphosphate

Other ion exchange applications

Zeolites with good selectivities for Cs and Sr are available
used to remove 137Cs and 90Sr from radioactive waste streams
concentrate waste prior to disposal

more robust than organic ion exchange resins

not susceptible to radiation damage

Separations
Gas separations such as O2/N2 Straight chain hydrocarbons from branched chains using Ca-A
straight chains are a problem for diesel fuel straight chains are useful for detergents

Water from organics

extraframework cations coordinate to the water and remove it from the organic phase

Silicon to aluminum ratio and hydrophobicity

Zeolites can be prepared with varying silicon to aluminum ratios High silica zeolites are hydrophobic
they are not wet they can select hydrocarbons from mixtures

Low silica zeolites are hydrophilic

Hydrocarbon separations
Zeolite A can be used to separate straight chain hydrocarbons from a mix. Straight chains used to make detergents

Ca/Na - A

O2 / N2 separations
N2 is adsorbed more strongly than O2 in zeolites with a low Si/Al ratio This is a consequence of the quadrapole moment of N2 interacting with the extraframework cations Used for gas separation but it has the disadvantage of being a batch process

Catalysis
Zeolites are frequently used as acid catalysts
ion exchange zeolite so that extraframework cations are protons ion exchange zeolite so that high charge extraframework cations bind water and release protons Lewis acidity at defect sites

Can do carbenium ion chemistry

Catalysis with zeolites

The majority of the applications make use of the acidic properties of zeolites Acid sites can be introduced by ion exchange for NH4+ followed by thermal decomposition Alternatively, acid sites can be introduced by ion exchange for La3+ followed by cation hydrolysis reactions
Ln3+ + H2O ----> Ln(OH)2+ + H+

Dewaxing
Unbranched hydrocarbons have high melting points and tend to form waxes. Wax forming compounds in fuels are undesirable Unbranched hydrocarbons can be selectively cracked in the presence of branched hydrocarbons using ZSM-5

Xylene isomerization
p-xylene is needed for the production of polyesters Xylenes can be rearranged over ZSM-5
can selectively obtain p-xylene

The production of p-xylene

Isomerization is used as part of a cycle that separates p-xylene from other compounds

Transalkylation with xylenes

Transalkylation is an unwanted side reaction during xylene isomerization

Transalkylation using toluene

Toluene can be converted to a much more valuable mixture of xylenes and benzene over ZSM-5
+

Alcohol dehydrations
Alcohols can be dehydrated to give alkenes
selectivity depends on pore size

Gasoline and zeolites

Most gasoline is processed using Faujasite type zeolites
high molecular weight materials are cracked second largest application of zeolites

Gasoline can be made by the dehydration of methanol over ZSM-5!!

Mobile MTG process only used in New Zealand

Synthetic gasoline
ZSM-5 is capable of transforming methanol to high grade gasoline by dehydrating the alcohol Proceeds via dimethyl ether Not economical is most western nations

Fluid Catalytic Cracking (FCC)

FCC is the most important industrial application of zeolites Carried out using zeolite Y High molecular weight hydrocarbons are broken down into lighter fragments This cracking process is an acid catalyzed carbenium ion rearrangement Zeolite inhibits formation of coke etc. .