ZEOLITE CATALYSTS IN GREEN CHEMISTRY

Dipak Kumar Chakrabarty Professor Emeritus INDIAN INSTUTUTE OF TECHNOLOGY, BOMBAY MUMBAI 400076

A positive development of the twenty first century is that we have woken up to the danger to our future - the danger to our environment created my mindless industrial expansion of the last century.

In the year 1987, the World Environment Commission published a report Our Environment that emphasized the need for sustainable development. Sustainable development means development to fulfill the needs of the present generation without endangering the needs of the future generation. The concept includes many aspects of which utilization of renewable resources and protection of the environment is primary. The traditional concept of process efficiency that considered product yield as the main criteria is being replaced by including such considerations as elimination of waste and protection of environment.
This has brought the concept of GREEN CHEMISTRY producing chemicals With minimum damage to the environment .

Green Chemistry
Chemical Industry has its share in polluting the environment and today it has realized that the time has come to make the industry more and more efficient not only in terms of profit and yield, but more accountable in terms of pollution abatement and eco-friendliness. This has led to the term GREEN CHEMISTRY.
Traditionally, organic synthesis is highly logical, but highly inefficient. This situation was allowed to continue mainly because 1. The scale of production was not very large, 2. Organic chemists were not much concerned with catalysis. 3. Short life cycle of the products and the processes.
Situation has changed since then and more and more organic chemists are taking the catalytic route. Our concern here will be zeolite catalysts.

Briefly, Green Chemistry is

Efficient use of (preferably renewable) raw materials, Elimination of wasteful byproducts, Avoiding use of toxic/hazardous reagents and solvents, Use of safer final (biodegradable) products, and Increasing energy efficiency.

Two considerations that dominated green chemistry are:

A.Maximum atom utilization, B.The minimum waste produced (E Factor). The waste includes byproducts, reagents, solvent loss and even fuel.

E FACTOR
In simple form, it defined as: (Chemicals in (kg) - Desired product (kg) ) / Total product (kg) The enormous waste in different segments of industry are shown in the table below. Industry segment Oil refining Bulk chemicals Fine chemicals Pharmaceu ticals Product, tonn/anum 106-108 104-106 102-104 10 - 103 kg waste/ kg product <0.1 <1-5 5-50 25-100

M. Lancaster, Green Chemistry : An Introductory Text, Roy.Soc.Chem., cambridge, 2002.

Q FACTOR
Another important parameter is the extent of harmfulness of the waste. For example, sodium sulphate as a waste is certainly far less harmful than a cyanide waste. A new term environment quotient (Q) has been coined to emphasize this difference and some number has been arbitrarily assigned to different wastes according to their extent of their harmful effect.
R. A. Sheldon, Chemtech., 38, (1994).

Some examples of atom utilization

3PhCH(OH)CH3 + 2CrO3 + 3H2SO4 3PhCOCH3 + Cr2(SO4)3 + 6H2O atom efficiency = 360/860 or 42% catalyst 3PhCH(OH)CH3 + O2 PhCOCH3 + H2O atom efficiency = 120/138 or 87% C2H2 + 1/2O2 C2H2O atom efficiency = 100%
The idea was first introduced by Trost. See B. M. Trost, Science, 254, 147 (19910.

Zeolite Structure

Zeolites are crsytalline alumino-silicates with exchangeable cations The cations can be exchanged with protons that make them acidic solids. Si:Al ratio can vary in zeolites from 1 to infinity. Number of acid sites decreases with increase in the Si:Al ratio Strength of the acid sites increases with the Si:Al ratio. There are also Lewis acid sites (tri-coordinated Al). They have micro-pores of entry port size varying from about 3 to 12 A.

Zeolite Pore Structure

Zeolites are formed by oxygen-sharing T (Si or Al) atoms, each T atom linked to four oxygen making tetrahedra. These tetrahedra are linked to form rings containing equal number of oxygen and silicon atoms. The rings share common oxygen (or silicon) forming different polyhedra. The polyhedra then join by sharing common oxygen (or silicon) forming the three dimensional network structure giving rise to pores. The pores may be all in one direction or may run in several directions.

Each corner is a Si atom and oxygen atoms are at the middle of each edge. a: sodalite polyhedron; b: zeolite sodalite; c: zeolite A; d: faujasite

Five-member silicon-oxygen ring. Oxygen sharing between rings formation chain.

a: Chains joining to form 10-Oxygen pores in ZSM-5; b: three-dimensional pore structure of ZSM-5 showing zigzag structure

Pore openings in a: Ferrierite and b: ZSM-23

8-Oxygen, 10-Oxygen and 12-Oxygen rings found in erionite, ZSM-5 and faujasite.

Table 2. Pore size of zeolites.

Pore type

No. of O atoms in the ring 8 10

Framework structure

Pore size, A

Dimensionalit y

Small medium

ZEOLITE A ZSM-5 ZSM-11 SAPO-11 X, Y MORDENITE BETA SAPO-5 L SAPO-8 VPI-5 CLOVERITE

4.1 1.x 5.4 5.4 x 5.3 6.3 x 3.9 7.4 7.0 x 6.5 7.5 x 5.7 7.3 7.1 8.7 x 7.9 12.1 13.2 x 6.0

3 3 3 1 3 2 3 1 1 1 3 3

Large

12

Extralarge

14 18 20

A major application of the zeolites in catalysis is in acid catalyzed reactions such as alkylation, acylation, electrophilic aromatic substitution, cyclization, isomerization and condensation. We shall take some examples here.

Catalysis with acidic zeolites

1. ALKYLATION Mobil-Badger Process (Polyalkylation is suppressed)
+ C2H2 HZSM-5

Similarly, propylbenzene could be manufactured using a 3-dimensional dealuminated mordenite (3-DDM) catalyst
dealuminated mordenite Si/Al = 100-1000

Dealumination enabled to obtain very high Si:Al ratio (up to 1000). In these form, the micropores of mordenite were connected through mesopores (5-10 nm).
K.Tanabe and W.F. Holderich, Appl.Catal.A General, 181,399 (1999).

Naphthalene is dialkylated with propene over 3-DDM. The product is used in making the carboxylic acid that is an important monomer for making plastics.
+

G.R. Meima, G.S. Lee and J.M. Garces, in Fine Chemicals Through heterogeneous Catalysis (Ed. R.A. Sheldon, Wile-VCH, Weinheim, 2001.

Acylation
Acylation with heterogeneous catalysis ismuch more difficult because of the polarity difference of the substrate and the acylating reagent that makes it difficult to achieve Favourable adsorption ratio of the two. This could be achieved by the use of H-Beta.
O + (CH 3CO)2O

A. Vogt and A. Pfenninger, EP0701987A1, 1996 to Uetikon AG.

Hydroxyalkylaton using zeolites is difficult because of unfavourable adsorption ratio of the reagent and the . substrate. This difficulty is avoided by having the aromatic and the epoxide functions in the same molecule
H-ZSM-5 or H-Beta O

J.A. Elings, R.S. Downing and R.A. Sheldon, Stud.Surf.Sci.Catal, 105, 1125 (1997).

Ce3+ exchanged Y zeolite could catalyze toluene and xylenes using with higher carboxylic acids showing that free carboxylic acids can be used in acylation.
O R

RCO2H

B. Chiche, A. Finiels, C. Gauthier, P. Geneste, J. Graille and D. Pioch, J. Org. Chem., 51, 2128 (1986).

Formation of N-heterocycles by intermolecular cyclization is catalyzed by acidic zeolites. Synthesis of pyridine and picoline from a mixture of acetaldehyde, formaldehyde and ammonia in presence of H-ZSM-5 is an example.
CH 3CHO + HCHO + NH 3 H-ZSM -5 H 2N NH2 N H + N Pd N N

M.J.Burk et. Al., J. Org. Chem., 64, 3290 (1999)

Beckmann rearrangement
produces 2 kg 0f ammon. sulfate per kg of product sulfuric acid O NOH
Sumitomo conv entional

NH

H-ZSM -5
Si : Al > 1000, 350oC v ap. phase

W. F. Holderich et al. in Fine Chemicals through Catalysis, pp.217 -231, Wiley-VCH, (2001)

Epoxide reaarangement ( key step in the manufacture of many intermediates in the fine chemical industry. Traditional method used stoichiometric Lewis acids or bases.
O H TS-1 or ZSM -5 O TS-1 ZSM -5 conv. 100% 99% select. 98% 97-100%

G. P. Heitmann, G. Dahlhoff and W.F.Holderich, J.Catal, 186,, 12 (1999) Traditional method for preparing 2,6-dichlorobenzonitrile uses stoichiometric Amonts of chlorine, HCN and POCl3 with atom efficiency 31%. The new process Was developed uses zeollite catalysts Eur.Pat.Appl. EP948988 (1999)
Cl + Cl 2 Ag-H-M or 350 oC Cl Cl

Cl

CN Cl Cl NH 3 + O 2 catalyst 350-450 oC Cl adsorption in faujasite Cl Cl Cl Cl

K. Iwayama, S. Yamakawa, M. Kato and H. Okino, Eur. Pat. Appl. EP948988 (1999) to Toray

Oxidation
Traditional methods of oxidation in organic chemistry uses stoichometric reagents (salts of manganese and chromium. The new chemistry tries to use molecular oxygen or hydrogen peroxide. TiO2 supported on silica was not effective with hydrogen peroxide because the water produced gets strongly adsorbedo on silica. TS-1 has been used successfully because this titanium substituted silicalite-1 is hydrophobic. Phenol is converted with hydrogen peroxide to a mixture of hydroquinone and catechol. Rhone-Poulenc Process uses perchloric acid and phosphoric acid whereas Enichem process uses TS-1. A comparision Is given here
Table 3. Comparision of phenol conversion processes Process (catalyst) Phenol conversion (%) Selectivity on phenol Catechol/hydroquinone Rhone-Poulenc (H3PO4,HClO4) 5 80 2.3 Enichem (TS-1) 25 90 1

TS-1 is also called a redox molecular sieve and can be used as a catalyst for many oxidations with hydrogen peroxide. In presence of TS-1, ammonia and hydrogen peroxide forms in-situ hydroxylamine which reacts with a ketone. An example is:
O TS-1 HO NHCOCH3 HO H+
Beckmann rearrangement

NOH + NH3 + H2O2

A. Corma, L.T. Nemeth, M. Rench and S. Valencia, Nature, 412, 423 (2001).

HO

paracetamol

Bayer-Villiger Oxidation (cinversion of ketone or an aldehyde to the ester

The peracid undergoes a nucleophylic attack on the carbonyl group givimg an inetrmediate. In the next step, a concerted migration of one of the alkyl groups takes place releasing the Carboxylate anion. The reaction is widely used in organic chemistry. Zeolite beta containing 1.4 wt% of tin is a good catalyst using hydrogen peroxide.

O 1 eq. H2O2 0.66 mol% Sn-Beta dioxane, 90 oC

O O

A lrge number of bulk chemicals are produced by using molecular oxygen either in the liquid or in the vapour phase reaction. S0me of these are: Benzene/ethene to styrene, p-xylene to terephthalic acid, formaldehyde to methanol, Ethene ot ethene oxide, n-butane to acetic acid, propene to acrylonitrile, n-butane to Malic anhydride, o-xylene to phthalic anhydride, isobutene to methyl methacrylate etc. Molecular oxuygen is a spin triplet and its direct reaction to a organic singlet compound is spin forbidden. To overcome this, the triplet is allowed to react with paramegnetic Metal ions forming a superoxo-metal complex that forms a variety of metal-oxygen species. Use of catalytic route to selective oxidation in presence of several functional groups is A big challenge.

Basic zeolites
Comarattively much less attention has been paid to basic zeolites. Zeolites can be made basic by 1.Exchange of protons with alkali or rare earth ions or 2. by depositing nano-particles of alkali or alkali earth oxides in the pores. The basic sites are weak. They can be used to generate C-C bond in the side chains of substituted aromatics.
CHO + NCCH2CO2Et Na-X CN COOEt

Chemicals through Hetero. Catal., Cormma and S. Iborra in Fine 309 (2001).

NH2 + (M eO)2CO

NHCH3 K-Y + M eOH + CO2

CN

+ M eOH

Cs-X

CN + H2O

SIDE CHAIN ALKYLATIONS

K.R. Kloestra, H. van Bekkum, Chem. Soc.Chem.Commun., 1005 (1995).