Recent trends in the applications of zeolites and molecular sieves for the synthesis of speciality and fine chemicals

T.S.R. Prasada Rao and G. Murali Dhar (Editors)

Recent Advances in Basic and Applied Aspects of Industrial Catalysis

151

Studies in Surface Science and Catalysis, Vol. 113 9 1998 Elsevier Science B.V. All rights reserved

R E C E N T T R E N D S IN T H E A P P L I C A T I O N S OF Z E O L I T E S AND MOLECULAR SIEVES FOR THE SYNTHESIS OF SPECIALITY AND FINE CHEMICALS S.J. KULKARNI Catalysis Group, Indian Institute of Chemical Technology, HYDERABAD-500 007, INDIA ABSTRACT Since 1980, the applications zeolites and molecular sieves in the speciality and fine chemicals increased enormously. Zeolites are being used in the various types of reactions like cyclization, amination, rearrangement, alkylation, acylations, ammoxidation, vapour and liquid phase oxidation reactions. Zeolites and molecular sieves have also been used to encapsulate catalytically active co-ordination complexes like ship-in-bottle and as a support for photocatalytic materials and chiral ligands. Redox molecular sieves have been developed as an important class of liquid and vapour phase oxidation and ammoxidation reactions. We have discussed few typical recent examples of various types of reactions. Key Words

9

Zeolites, molecular sieves, speciality chemicals, fine chemicals, redox molecular sieves, ship-in-bottle. 1.

INTRODUCTION

Zeolites are uniform porous crystalline aluminosilicate type catalytic materials. The tetrahedral silicon and aluminum, the atoms of the framework, are linked through oxygen atoms to form one/two/three dimensional zeolitic structures. The framework aluminum and silicon can be replaced by other elements like phosphorus, germanium, gallium, titanium, vanadium, etc. to form various molecular sieves. The various zeolites with respect to pore dia are depicted in Fig.1. Zeolites are widely used in the petrochemical processes. Since 1980, the zeolites and molecular sieves are being used in the syntheses of speciality and fine chemicals due to their properties like activity, selectivity, thermal stability, reusability, noncorrosiveness, for the ease of separation and handling and ecofriendluy nature of the processes. A number of reviews have been published in the literature discussing various applications of zeolites.[1-10 ] Typical recent examples based on our work [11-33] and literature will be discussed.

152

Poro sloe

~rB 11o-loo

(A)

"size

"(A)

14

14

12

12

10

lO

8

4 2

1950

1960

1970

1980

1990

year

Fig. 1. Evolution in ziolite / molecular sieve

2. 2.1

ACID--CATALYZED REACTIONS Cyclization reactions: We have reported a number of cyclization reactions. The one- and two-N containing five and six-membered, saturated and unsaturated heterocycles were synthesized from CI to C5 aliphatics like alcohols, aldehydes, ketones, in presence of ammonia and other amines [11-33]. For example, 3,5-1utidine was synthesized from propionaldehyde or propanol, formaldehyde and ammonia over modified ZSM-5 catalysts. The yield of 3,5-1utidine was in the range of 40 to 65 wt% at 60-90% conversion of propionaldehyde over modified ZSM-5 catalysts at 400~ In the reaction of ethanol, formaldehyde and ammonia over ZSM-5 catalyst pyridine and picolines were obtained. The reaction route or mechanism is shown in Fig. 2 and 3. In the reaction of acetaldehyde, formaldehyde and ammonia over ZSM-5 pyridine and 3-Picoline were obtained. On the other hand, 2- and 4-Picolines were obtained in the reaction of acetaldehyde and ammonia. The acylative cyclization of phenol with acetic anhydride was carried out over CeY type zeolites. The reaction mechanism is given in Fig. 4. At 380~ the yield of 4-methyl coumarin was 75 % at 81% conversion of phenol. N-Methylpyrrolidine was synthesized from 1,4-butanediol and methylamine over Cr ZSM-5 and modified ZSM-5 catalysts at 300~ The reaction mechanism is given in Fig. 5. The synthesis of a number of five- and six- membered heterocyclics have been depicted in Table 1. The reaction was carried out at 250-400~ at 30-80 hydrogen atm., under down-flow fixed bed conditions. The yield of Nmethyl piperazine was 90% at 95% conversion over ZSM-5 catalysts. Similarly 2-methyl pyrazine and piperazine were synthesized from propylene glycol and ethylenediamine over HZSM-5 ( Fig. 6 ).

153 .Ic~H3CH20H -4-[HCHO] 4- NH3

CH3CHO

u,,

CH3CH2NH2

"-.,

i/ [ CH3CH 9NH ] i MINE

CH=NH

H3C

(o)

-t-CHII CH3 Nil

HCHO -NH3~

- H2 =

-H-~O

PYRIDINE

CH= NH (b)

H3C

4-

H~C--CH%NH

I~H3-2NH~

IHC~N

"~NH

( - H 2 = H3C~

3

2- PtQ3LINE

Fig.2. Synthesis of pyridine and pic01ines from ethanol (Ref. 20)

CH3CF2 'I 0H

CH3CH2-C--H 0

4-

HCHO

+

HL:,O

-I-CH3CH,~CHO CH3-CH2-ICIH

CH3-CH?_-CH

c~- CH- CH

NH

0

1 -I..CL~50H

I+NH3

H3G\CH; CH~'cH I

HN~.CI..IfcH2

I

-2H

..CH~ H3C H3Cx

CH /N CH2

I 2H2

0 Fig. 3. Synthesis of pyridine and picolines from ethanol : Reaction mechanism (Ref.20)

154

,OC~N~ OH

+

c~co +

c.~coo-c~No~

~OTo CeNaY

~

+

+[ +

Cel~Y

H20 Fig. 4a. Plausible reaction mechanism (Ref. 15)

_ ~ OH '

+

(CH3CO)20

~ c~ O

[

~ ' ~ 0 4 - METI'iYLCOUMARINE

~OH

CeNaY ~-~OCeN~

~- ~ / O c O C H 3

O

COCH3

O

CH 3 Fig. 4b. Synthesis of 4-methyl coumarine (Ref. 15)

OCOCH3

ol

155 H0 ~ ~ " ~k"~ ~ H 2 HO~(~H I / CrZSM_5

/ REACTANT

-

H0 ~ / . ~ / ~ /

+ NH2CH3

/

/

H

/

"ICrZSM'5] / *L1,H~~ V' "r,-----''~-~'1"l (HO)CrZSM-(:-::~ ..

+

H+

H20 "-..~"v"~ NHCH3

L7

f,

H20

H2 H+

+,,v,.,,,./N HCH3

J

L~J

PRODUCT I

0-13

Fig. 5. Plausible reaction mechanism to.from THF and N-methyl pyrrolidine (Ref. 18)

HO -I- CH?_.+nOH 4- R-NI-I~ .

"-

-II

n =40RS,R--'-CH 3 OR CH2GI-I3

HO / \CH2

CH2

~..0

+ HO-I-CH2-1-n NHR

R M= Cr, V, Mn, MO,

CH2 CH2 /

~ OH -I-- CH3NH2 I

CH3 N-MEZHYL / PYRROLIDIN

156 Table- 1 Cyclisation of different substrates over CrZSM-5 ~ SI. No.

Substrate-I

Substrate-ll

Time on stream

(h) I.

HO~,~

NH 3

4

CH3NHz

3

CHsCH3NH2

3

OH

2.

HO~ OH

3.

H O ~ HO~ / ~ T N

6.

HO~

C6HsNHz

48.0

NCH

64.2 59.6

4

94.0 [~O

CH3NH2

1

CHsNHz

2

OH

HN(CHzCHzOH)2

NH

C C ~

OH

5.

Yield (%)

NCH CH 2 3

OH

4.

N-contained cyclic product

A

L. NCH3 /--N

H~CN

31.2

41.0 NCHz

N_J

d

7.

CH3NH2

4

C

48.0 NCH3

8.

~

CH3NH2

CH3NH2

~~

o II

C

9.

I0.

4

--o

OH

e

3

3

--- 100.0

NCH

No reaction

38.0

a: C4ZSM-5 = 4.0 g; The molar ratio of substrate-I to substrate-II is 0.25; W.H.S. = 0.5 h a, Temperature = 300~ The conversion of substrate-I is 100 % (unless stated Major side products are O-containing cyclic compound and in traces of amino alcohol b: Substrates are in 1" 1; c: Other major product is l-methylpiperazine; d" Conversion of THF is 64%; E 9 Conversion is 43%. (Ref. 19)

157 CH CH2

CHzOH

2 - MKTHY1.PYRAZINE 4-

ETHYLENEDI AIvflNE

-.

2 --METHYl_ PIPERAZINE

CliO +

\

IH3 CHOH

AROMATICS

CH

II CHOH

I ]Ha

,~"

-H +

CIH / CIHOH 4" ~ H2- NH2

~7.. S ~ ~ ~ O

''~

CH2 I

~Ha NH2

CH I "~O 4- EDA -----,P 2rap + PIPERAZINE+ AROMATICS CH 2

~H3 CO I

O-t3

ClH3 -

O

II (CH3)2 - C "-CH-C ~- CH--C --CH 3

I

H I FN'(CH~ ~N /

P RODUC~S

1 -~

Ha

Fig. 6. Differentreaction routes in the reaction of propylene glycolwith ethylenediamin (EDA) over HZSM-5 Catalyst. (Ref. 1I)

2.2.

Other reactions: Zeolites having compensation cations like H + , La 3+ , Fe 3+, etc. are acidic in nature. The wide variety of reactions which can be catalyzed by Bronsted, Lewis acids or metal cations can be carried out over zeolites. For example, isomerization of aniline to 2-methylpyridine occurs at 510~ over HZSM-5. Some of the isomerization reactions reported in the literature are o- and p- toluidines to m- ( o- & p- ) toluidines; the conversion of tetrahydrodicyclopentadine to adamantine over REX. The alkylation of phenol, naphthalene, or naphthol with methanol have been carried out over zeolites. The alkylation of aniline, thiophene and pyridinewith methanol have been reported over modified Y and HZSM-5 zeolites. The acylation of toluene, phenol have studied. The following rearrangement reactions have been carried out, the conversion of 2-phenylpropanal to phenylacetone, dihydro-5(hydroxymethyl)-2-furanones to 3,4-dihydro-2-pyrone, the Beckmann rearrangement of cyclohexanone oxime to caprolactum, etc. The reactions carried out in our laboratory are summarized in Fig. 7. Various dehydration reactions have also been carried out over zeolites. Similarly many ring transformation, halogenation reactions have been reported. 3.

BASE-CATALYZED REACTIONS

The base-catalyzed reactions were carried out over Na, K, Cs modified Y zeolites; for example the conversion of toluene to ethylbenzene and styrene in presence of methanol over CsY zeolite. Also the side chain alkylation of picolines with methanol was carried out over CsY. CsY is also used in the synthesis of 4-methylthiazole from acetone, methylamine and S02.

158

I Liquid phase oxidation reactions

Synthesisof ' ~ (1). 2-Methl-Naphthaquinone \ (2). Anthraquinone \ (3). Cyclohexanone \ (4). Pyridine-2-carboxaldhyde \ \ \ \ \ \ \

[ i. Alkylati~ I

~

/ ~ ~

/

/

/

/

/ //

~ ~ ~Pro_ce~se;,~~ , , , .

Synthesis of ~ \ / [ (1) 2-methyl-napthalene / ] (2) 2,6-dimethyl-napthalene / [ (3) 2,6-diisopropyl-nU ]

\

~

/

Cyclisation~' 1 '

Synthesisof (1) pyridine,3-picoline (2) 2-picoline,4-picoline (3) 2,6-Lutidine (4) 3,5-Lutidine (5) 2,3,5-collidine (6) N-methyl-pyrrolidine (7) N-methyl-pyrrolidone (8) Piperidine,N-methyl-pyrrolidine (9) Piperizine,N-methyl-pyrrolidine (10)y-buthyl-pyrazme

I

~ ~

[ Acr,atio. r

Amination[

Synthesisof (1) methyl& dimethylamide (2) Benzonitrile (3) Acetonitrile

I earra. eme.t 1

Synthesis of

(1) 4-methyl-coumarin (2) Anthraquinone (3) ortho& para-acetyl phenols

/

] 71 /

Synthesisof ,

(1) ortho-acetyl-phenol (2) Phenyl-diamine (3) Beckmann

Oxidation & Ammoxiation Synthesis of (1) 4-cyano-pyridine (2) 3-cyano-pyridine (3) Benzonitrile (4) Acetonitrile (5) F;'ridine-2-carboxaldhyde Fig. 7. Catalysts & Processes for specilaity & fine chemicals (1990-1996)

4.

BIFUNCTIONAL ZEOLITIC REACTIONS

Typical reaction in this category is the conversion of limonene to P-cymene over PdH-borosilicalite where isomerization is followed by dehydrogenation. Also many reactions mentioned here, particularly catalyzed by transition metal ion or bimeallic, are bifunctional zeolitic reactions. 5.

OXIDATION REACTIONS

In the liquid phase reaction of phenol with H202 in presence of titanium silicalite (TS-1), catechol and hydroquinone were obtained. This is the first reaction commercialized using the redox molecular sieve. A number of oxdation, hydroxylation and similar type of reactions were reported over Ti, V-, Cr, etc. silicalites, Ti, V, Cr, silicoaluminophosphates, TiY, Til], etc. molecular sieves (Fig 8. ). Typical liquid phase reactions which we have carried out are given in Fig. 7.

159 (R.A. Sheldon/Journal of Molecular Catalysis A: Chemical 107 (1996) 75-83~ OH

~

~.OH

OH /

o

~]

NOH

R=CO ~.~.,~,.~',~

~

o

R= I R,CHOOH

~, R,COH

.

o,or',

o,

~,)

ArCOR

~"

-

R=CO

!

,/O~

RCH--CH=

"~V~RCH"-- ell_ ~

~

9

R CO

=

Fig. 8a. Oxidations catalyzed by TS-1

U ~ Fig. 8b. Selective oxidations catalyzed by CrAPO-5

I) IRONPHTHALOCYANN I(F EePc)IN(~orOZEOLITE

N

Fe

Fe (Pc)

N

HYDROQUINDNE

H20+ R I/l,,.

0

(

..~

"

~

Pd(U}O ~ ~H '~~0" ~Fe(Pc) Pd(O) +2 H +

0

FelPc) or I/2 Fe (Pc)

H20 I/2 0 2

0 Benzoquinone

Triple catalytic system for o,-ddation of terminal olefins i) Oxidation of alkanes with tetrabutylhyropero,'dde ii) Zeolite Y encapsulated Mn-salen N, N'-ethylene bis (salicylidenaminato) is used in the epo:ddation of oletins with iodosy,benzene Fig. 9. Metal complexes encapsulated in zeolites-enzyme-mimics ship in the bottle catalysts

160 0

METAL COMPLEXES ENCAPSULATED IN ZEOLITES: SHIP-IN THE BOTTLE AND ZEOZYMES

Iron-phthalocyanine (Fe-Pc) encapsulated in Y and VPI-5 zeolites were used for the oxidation of alkanes or olefins in presence of t-butylhydroperoxide or H202 (Fig. 9). Fe-Pc-Y also catalyzed the oxidation of cyclohexane to cyclohexanol and cyclohexanone with tbutylhydroperoxide ( TBHP ). Ruthenium perfluorophthalocyanine complexes encapsulated in NaX ( Ru-F16 Pc-X ) were active for the oxidation of cyclohexane with TBHP at room temperature.Manganese(II ) bipyridyl complexes in faujasite ( Y ) zeolite are active for the oxidation of cyclohexene to adipic acid in the presence of H202 at room temperature. Similarly oxidation reactions have been reported using copper complexes encapsulated in X,Y, and VPI-5 molecular sieves. 7.

ENANTIOSELECTIVE REACTIONS.

The conversion of 2-phenylbutene to 2-phenylbutane and acetophenone to 1-phenylethanol over HZSM-5 modified by Pt and a chiral ligand has been reported. An asymmetric hydrogenation of N-acyldehydrophenylalanine derivatives with enantioselectivities 95% over zeolite-suported chiral rhodium complexes has been reported.

8.

P H O T O C H E M I C A L REACTIONS:

The material like TiO2 has been dispersed in the zeolites like X, Y and photocatalytic reactions have been carried out like ethylbenzene to acetophenone and various oxidation reactions. Thus zeolites and molecular sieves are of wide utility, eco-friendly, fascinating and ever-increasing in the syntheses of speciality and fine chemicals. REFERENCES

.

9. 10.

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