Index

1. Abstract
2. Introduction
3. Problem statement
4. Literature review
5. Experimental
a. Synthesis of catalysts
b. Characterization of Catalysts
c. Catalytic Activity Study
6. Future plan
7. References
 Index
Abstract

Introduction

Problem statement

Literature review

Synthesis of catalysts

Characterization of Catalysts

Catalytic Activity Study

Future plan

References
Abstract
In this work, gas-phase alkylation reactions of m-cresol with iso-propanol to form
pharmaceutically important product thymol using highly efficient metal ion-exchanged
Silica-Alumina framework (SAL) catalysts is reported. Environmentally benign SAL
catalysts were prepared by ion-exchange method and characterized by XRD, N 2 sorption,
SEM, and TEM techniques.
Catalytic activity of the reaction to optimize different reaction parameters like degree of
metal loading, reaction temperature, WHSV, reactant mole ratio and catalyst loading to
obtain the maximum selectivity to desired product thymol will be investigated in future
work.
 Introduction...
● Alkylation of m-cresol with iso-propanol is an important acid catalyzed Friedel-Crafts reaction. The
main product is 2-iso-propyl-5-methyl phenol, also known as thymol.
● Thymol is a precursor of the industrially important pharmaceutical product called menthol,
antioxidants, insecticides, insect and animal repellents, fungicides, medical disinfectants, etc
● Other products like iso-propyl 3-methylphenyl ether (IPMCE), 4-isopropyl 3-methylphenol
(4I-3MP), 3-isopropyl 5-methylphenol (3I-5MP), dialkylated m-cresols are also widely used as
additives in food industry, perfumes, food flavorings, mouthwashes, pharmaceutical and cosmetics.1

Several studies on the iso-propylation of m-cresol have been reported till date using both homogeneous
(mineral acids, Lewis acids, etc) and heterogeneous catalysts (mesoporous materials, metal oxides, etc). 2,3
● Mineral and Lewis acids possess severe environmental problems as well as low Product selectivity.8
● Metal oxide become rapidly deactivated due to leaching of active metals and pore blocking.
Introduction
Need to develop environmentally friendly catalysts with tunable acid densities and pore volumes for the
selective production of thymol.
Hence, the metal-loaded SAL catalyst with different amount of metal loadings and controlled Bronsted
and Lewis acid sites is to be developed.

Herein, we report gas phase alkylation of m-cresol with iso-propanol in fixed bed reactor over different
metal ion-exchanged SAL catalysts to selectively produce thymol.
● Different amount of zinc is loaded in multiple ion-exchange steps over SAL catalysts
● Synthesized catalysts were characterized by using XRD, SEM, TEM, and N2 sorption techniques.
● Design of experiments (DOE) method is implicated to optimize the process parameters like
temperature, reactant mole ratio, WHSV and catalyst loading for this alkylation reaction.
Figure 1: Reaction scheme for alkylation of m-cresol with iso-propanol
Problem Statement
For the selective synthesis of thymol, high Lewis acidity is required in the alkylation of
m-cresol with iso-propanol. From earlier reports, it is known that among different
transition metals exchange with protons present on SAL zeolite, Zn-SAL with high Lewis
acidity gave the highest selectivity to thymol.
● Now determining the amount of zinc on SAL catalysts by multiple ion-exchange
steps is important to achieve highest catalytic activity.
● Moreover, optimization of process parameters is also necessary.
Table 1. Literature review

Reactant Catalyst Reaction parameter Conversion Selectivity Reference

Literature Review T= 360 0C
m-cresol: propylene Activated alumina P= 50 bar 75 (m-cresol) 80 Biedermann et al.4
t= 4 h
m-cresol: iso-propyl T= 300 oC, P= 1 bar K. Shanmugapria1
80.9 (m-cresol)
acetate (1:3) Al-MCM-41(55) WHSV= 1.52 h-1 83.7

m-cresol: IPA T= 300 oC, P= 1 bar

Al-MCM-41 55 (m-cresol) 75.3 Umamaheshwri et al. 5
(1:4) WHSV= 1.76 h-1
T= 400 oC, P= 1 bar
m-cresol: IPA (1:4) Mg-Al hydrotalcites 40 (m-cresol) 80 Velu et.al. 6
WHSV=8.6 mol/h-Kg
T= 255 oC
m-cresol:IPA (1:5) ZnAl2O4 78.2 (m-cresol) 88.4 Grabowska et al.7
P = 1bar
m-cresol: IPA Fe that contains Cr, T= 420 oC, P= 1 bar
17 (m-cresol) 60 Grabowska et al. 8
(1:5) Si & K oxides WHSV=1.5 cm3/h
T= 180 oC
m-cresol: IPA UDCaT5
P= autogenous 92 (IPA) 79 Yadav et al. 9
(5:1) (0.05 g/cm3)
t= 1 h

T= 200 0C, P= 1 bar

m-cresol: IPA (1:2) H-beta zeolite 60 (m-cresol) 40 Nie et al. 10
TOS= 15 min
Experimental: Synthesis of catalysts

● Ion-exchange method was used to load metal ions on the SAL catalyst.
● 0.05M aqueous solution of metal salt is mixed with SAL catalyst, keeping the liquid
to solid ratio 10.
● The mixture was refluxed for 24 h, then filtered, washed and dried at 120 °C for 8h.
● The samples were divided into two parts: the first one is calcined at 540 °C for 4 h
whereas the second one is used in the next ion-exchange step.
● For multiple ion-exchanges, the above steps were repeated and the calcined samples
were designated as Zn-SAL-N, where N is the ion-exchange step number.11
Experimental: Characterization of Catalysts
The average crystallite size (t) of the catalysts is
calculated by Debye-Scherrer formula:
t = kλ/βcosθ
Where, k = shape factor = 0.9,
λ = X-ray wavelength of Cu Kα radiation (1.54Å),
θ = Braggs diffraction angle,
Β = full width at half maximum height (FWHM) of
the diffraction peak.

The average crystallite sizes are:

H-SAL = nm
Zn-SAL-I = nm
Zn-SAL-II = nm
Zn-SAL-III = nm
Zn-SAL-IV = nm
Figure 2: XRD pattern of the prepared catalysts
Experimental: Characterization of Catalysts
BET Surface Area by N2 sorption
The surface area and micropore volume of the catalysts used in this work were measured by N 2
sorption techniques. The exchange of proton in SAL with Zn2+ cations decrease the surface area and
micropore volume due to the preferential location of exchanged Zn2+ inside the micropore of the SAL.
Table 2. Textural properties of the prepared catalysts

Specific surface area, SBET Total pore volume (P/Po=0.99) Micropore volume (cm3 Average pore diameter
Catalyst
(m2 g-1) (cm3 g-1) g-1) (nm)

H-SAL 382.2249 0.869204 0.127030 59.5675

Zn-SAL-I 367.6021 0.703383 0.113158 76.5374

Zn-SAL-II 327.7957 0.691148 0.094418 84.3389

Zn-SAL-III 309.1342 0.641033 0.093935 86.9456

Zn-SAL-IV 298.8266 0.610004 0.07734 89.6532

Experimental: Characterization of Catalysts
Scanning Electron Microscopy (SEM)
SEM images of all the catalysts revealed a polygonal morphology. In Zn-SAL, most of the Zn is
present in agglomerated form and the agglomeration increases with increase in the zinc content.

Figure 3. SEM images of catalysts (a) H-SAL, (b) Zn-SAL-I, (c) Zn-SAL-II, (d) Zn-SAL-III, and (e) Zn-SAL-IV
Experimental: Characterization of Catalysts
Transmission Electron Microscopy (TEM)
TEM image of H-SAL revealed its high dispersion due to high aluminium content present
in it. Whereas, when the zinc ions were ion-exchanged on H-SAL, the aggregation of the
particles was observed

Figure 4: TEM images of catalysts (a) H-SAL and (b) Zn-SAL-I

Experimental: Characterization of Catalysts
Energy Dispersive X-ray (EDX)
Figure 5 shows the EDX spectrum of H-SAL and Zn-SAL-I samples. In H-SAL, the
elements Si, Al, O, C and Cu were detected. Whereas Si, Al, O, Zn, C, and Cu elements
were detected in the sample Zn-SAL-I. This confirms the loading of Zn on SAL.

Figure 5: EDX analysis of catalysts (a) H-SAL and (b) Zn-SAL-I

 Experimental: Catalytic Activity Study
Design of Experiment
An experimental design using response surface methodology (RSM) is used to optimize
the process parameters in this continuous alkylation to minimize rigorous experimental
procedures and conserve the catalyst. The parameters, namely, temperature, reactant mole
ratio, catalyst loading, and WHSV on the conversion of m-cresol and yield of thymol will
be optimized using Box–Behnken design.
Table 3. Parameter levels and coded values used in the experimental design.

Range and levels

Factors Symbols
-1 0 +1

Temperature (°) X1 200 250 300

WHSV (h-1) X2 1.68 2.8 3.92

Reactant mole ratio X3 1 2 3

Catalyst loading (g) X4 0.5 1.0 1.5

 Table 4. Experimental design using Box–Behnken method

Run Temper Catalyst Reactant m-cresol Selectivity

Number ature WHSV Loading mole ratio Conversion to Thymol Run Temper Catalyst Reactant m-cresol Selectivity
Number ature WHSV Loading mole ratio Conversion to Thymol
1 0 0 -1 -1
15 0 0 0 0
2 -1 0 -1 0
16 1 -1 0 0
3 0 -1 -1 0
17 1 1 0 0
4 0 1 -1 0
18 -1 0 0 1
5 1 0 -1 0
19 0 -1 0 1
6 0 0 -1 1
20 0 1 0 1
7 -1 0 0 -1
21 1 0 0 1
8 0 -1 0 -1
22 0 0 1 -1
9 0 1 0 -1
23 -1 0 1 0
10 1 0 0 -1
24 0 -1 1 0
11 -1 -1 0 0
25 0 1 1 0
12 -1 1 0 0
26 1 0 1 0
13 0 0 0 0
27 0 0 1 1
14 0 0 0 0
Future Plan
1. Acidity estimation of the catalysts using ammonia-TPD and pyridine-FTIR technique.
2. Optimization of reaction parameters like temperature, WHSV, feed mole ratio and
catalyst loading for this reaction.
3. Development of kinetic model for this reaction.
 References
1. Shanmugapriya K. et. al., J. Catal. 2004, 224 (2), 347-357.
2. Zapata P.A. et. al., J. Am. Chem. Soc. 2012, 134, 857.
3. Yadav G.D. et. al., Microporous Mesoporous Mater. 2006, 89 (1–3), 16.
4. Biedermann W. et. al., Process for preparing thymol, US4086, 1978, 283.
5. Umamaheswari V. et. al., Journal of Catalysis, 2002, 210, 367.
6. Velu S. et. al., Research on Chemical Intermediates, 1998, 4 (6), 657.
7. Grabowska H. et. al., Applied Catalysis A: General, 2001, 220, 207–213.
8. Grabowska H. et. al, Res. Chemcial Intermed. 2001, 27, 281.
9. Yadav G.D. et. al., J. Phys. Chem. A, 2005, 109, 11080.
10. Nie L. et. al., Applied Catalysis A: General, 2012, 447, 14.
11. Afreen G. et. al., Molecular catalysis, 2017, 441, 122.
12. Marakatti V.S. et. al., RSC Adv. 2015, 5, 14286.