DECLARATION AND APPROVAL OF SUPERVISOR

I have prepared this report with inputs from my supervisor. I have taken care
of the formatting as per the guidelines circulated. I have not copied any section from
any other report, website or article.

SIGNATURE OF STUDENT

Report entitled “Catalytic conversion of methanol into low olefins over phosphorous
modified MCM-22” is approved.

SIGNATURE OF SUPERVISOR

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 ABSTRACT

Methanol to olefin process and its commercial potential is known for decades. It is used for
the production of low olefins such as ethylene and propylene. Low olefins are important
chemicals in the polymer industries, textiles industries and petrochemical industries. This
process has gained great attention because of the pricing and depletion of crude oil in future.
In the present work phosphorous modified H-MCM-22 is explored as promising catalyst to
enhance the lifetime of the catalyst and increase the selectivity of low olefins. HMCM-22 is
synthesized and modified with phosphorous by impregnation of HMCM-22 with aqueous
solution of (NH4)2HPO4 and subsequent calcination. The characterization of prepared
catalyst is done by using XRD, EDX, FTIR and SEM techniques. The phosphorus-modified
HMCM-22 samples and HMCM-22 are studied as possible catalysts for methanol-to-olefins
(MTO) reaction. The methanol to olefins (MTO) reaction was performed in a fixed bed
reactor over prepared catalyst and products were analyzed with the help of gas
chromatography equipped with flame ionization detector. Phosphorous modified HMCM-22
exhibits very good MTO performance, good resistance to deactivation by coke and 100%
methanol conversion with high selectivity to light olefins. The effect of modification of
phosphorous on H-MCM-22 as well as the various reaction parameters like temperature and
WHSV (Weight hour space velocity) on the selectivity of low olefins in MTO reaction was
found.

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 ACKNOWLEDGMENTS

I express my sincere gratitude to my supervisor Dr. Sreedevi Upadhyayula for her

invaluable and constant support throughout his academic carrier .Always I wonder about her
enthusiasm, systematic approach towards assigning the task and meticulousness towards its
progress. Her way of approach with the students is amazing and I would say, learning about
her extraction of work from the students is an art, so good and so smooth with her approach
everywhere.

I express hearty thanks B.Pradeep Kumar for his help in the experimental setup and
operation of GC, K.V Krishna Kishore and Tanmoy Patra who has shared work place with
me, helped me a great deal in my research work.

Finally and most importantly with all blessings of my parents ,I hereby express my hearty
and sincere thanks to all whoever supported me either directly or indirectly in completion of
my academic project successfully.

Mohit Jain

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TABLE OF CONTENTS

TITLE PAGE
ABSTRACT II
ACKNOWLEDGMENTS III
TABLE OF CONTENTS IV
LIST OF TABLES VI
LIST OF FIGURES VII
1 INTRODUCTION 1
2

2 REVIEW OF LITERATURE 3
2.1 ZSM-5 3
2.2 MCM-22 4
2.3 Zeolites advantages 4
4
2.4 Applications of zeolites
2.5 Catalytic Properties of the zeolites 5
2.5.1 Shape Selectivity
5
2.5.2 Acidity 6
8
2.6 The Methanol to olefins process (MTO)
2.6.1 History and overview of the process 8
2.7 Kinetic study
9
2.7.1 Results of catalytic reactions over ZSM-5 9
2.7.2 Results of catalytic reactions over H-MCM-22 10

2.7.3 Results of catalytic reactions over H-SAPO-34 11

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3 METHODOLOGY 12
3.1 Fabrication of quartz tube reactor and Methanol wick 12
13
3.2.Synthesis of HMCM-22
3.2.1 Hydrothermal synthesis of MCM-22 Catalyst 13

3.3 Synthesis of HMCM-22-X%P: 13

3.3.1. HMCM-22-%P Synthesis by incipient wetness method 13
3.4. Characterization of catalysts 14
15
3.4.1 Powder X ray diffraction (XRD) analysis 15
3.4.2. Infrared spectroscopy (FTIR) analysis 15
3.4.3. Scanning Electron Microscopy (SEM)
15
3.5. Experimental setup 16

3.6. Procedure 17

4 RESULTS AND DISCUSSION 18

4.1 Characterization 18
4.1.1 XRD 18
4.1.2 FTIR 19
4.1.3 SEM 19
4.1.3 EDX 20
4.2 Kinetic study 24
4.2.1.Effect of phosphorous loading on products distribution 24
4.2.2 Effect of temperature on products distribution 25
4.2.3 Effect of WHSV on products distribution 26
4.3 Results of catalyst testing 27
5 CONCLUSIONS AND SCOPE FOR THE FUTURE WORK 30
REFERENCES 31
APPENDIX-A1: SYMBOLS 33

LIST OF TABLES

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 Table-2.1: Results of activity testing on ZSM-5, Si/Al=30.
Table-2.2: Results of activity testing on H-MCM-22, Si/Al0=30.
Table-2.3: Results of activity testing on H-SAPO-34.
Table 3.1: Different frequency and their corresponding reasons

Table-4.1: EDX of prepared catalyst (HMCM-22)

Table-4.2: EDX of prepared catalyst (HMCM-22-1wt%P)

Table-4.3: EDX of prepared catalyst (HMCM-22-2wt%P)

Table-4.4: EDX of prepared catalyst (HMCM-22-1wt%P)

Table-4.5: Effect of phosphorous loading over HMCM-22 on product distribution

of MTO reaction

Table-4.6: Effect of temperature on product distribution on product distribution of

MTO reaction over HMCM-22-2%P.
Table-4.7: Effect of WHSV (Weight hour space velocity) on product distribution of
MTO reaction over HMCM-22-2%P.

LIST OF FIGURES

Figure-2.1: Pore size distribution of ZSM-5

Figure-2.2: Schematic pore size distribution in MCM-22

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Figure-2.3: Reactant shape selectivity of hydrocarbons
Figure-2.4: Product shape selectivity p-xylene
Figure-2.5: Transition state selectivity of methylethylbenzene
Figure-2.6: Bronsted acid sites in the framework structure of ZSM-5

Figure-2.7: Bronsted acid site in non-framework Structure ZSM-5

Figure-2.8: Schematic conversion of bronsted acid to lewis acid

Figure 3.1: Quartz reactor
Figure-3.2: Schematic procedure of MCM-22 by hydrothermal synthesis
Figure -3.3 Schematic procedure of HMCM-22-3%P by impregnation method

Figure-3.4: Experimental setup

Figure -3.5: Laboratory Experimental setup

Figure -4.1: XRD Patterns of Mo/H-ZSM-5 with different molybdenum loading

Figure-4.2: FTIR of prepared catalyst before calcination (MCM-22)

Figure-4.3: FTIR of prepared catalyst after calcination (MCM-22)

Figure-4.4: Scanning electron micrograph of MCM-22

Figure-4.5: EDX of prepared catalyst (HMCM-22)

Figure-4.6: EDX of prepared catalyst (HMCM-22-1wt%P)

Figure-4.7: EDX of prepared catalyst (HMCM-22-2wt%P)

Figure-4.8: EDX of prepared catalyst (HMCM-22-3wt%P)

Figure 4.9: Effect of phosphorous loading over HMCM-22 on the selectivity to low
olefins(C2 and C3) in MTO reaction at 450 °C, WHSV=0.2636, N 2 Flow rate
=25ml.min-1 and methanol flow rate =0.5 ml.h-1 after 15 minutes of time on stream.

Figure 4.10: Effect of temperature on the selectivity to low olefins (C 2 and C3) over
HMCM-22-2%P in MTO reaction at WHSV=0.2636, N2 Flow rate =25ml.min-1 and
methanol flow rate =0.5 ml.h-1 after 15 minutes of time on stream.

Figure 4.11: Effect of WHSV (Weight hour space velocity) on product distribution of
MTO reaction over HMCM-22-2%P at 450°C, N2 Flow rate =25ml.min-1 and methanol
flow rate =0.5 ml.h-1 after 15 minutes of time on stream.

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Figure 4.12: Effect of phosphorous loading over HMCM-22 on the selectivity to low
olefins (C2 and C3) in MTO reaction at 450 °C, WHSV=0.2636 and methanol flow
rate =0.5 ml.h-1 after 15 minutes of time on stream.

Figure 4.13: Effect of temperature on product distribution over HMCM-22-2%P in

MTO reaction at WHSV=0.2636 and methanol flow rate =0.5 ml.h -1 after 15 minutes
of time on stream.

Figure 4.14: Effect of WHSV on product distribution over HMCM-22-2%P at 450 °C

and methanol flow rate =0.5 ml.h-1 in MTO reaction after 15 minutes of time on
stream.

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