MCM-41 SUPPORTED NiO-MoO3 CATALYSTS

FOR HYDRODENITROGENATION OF SIMPLE

AMINES

A THESIS

Submitted by

S.J. SARDHAR BASHA

in fulfilment for the award of the degree
of

DOCTOR OF PHILOSOPHY

FACULTY OF SCIENCE AND HUMANITIES

ANNA UNIVERSITY : CHENNAI 600 025
MAY 2006

ii

ANNA UNIVERSITY : CHENNAI 600 025

BONAFIDE CERTIFICATE

Certified that this thesis titled MCM-41 SUPPORTED

NiO-MoO3 CATALYSTS FOR HYDRODENITROGENATION OF
SIMPLE

AMINES

is

the

bonafide

work

of

Mr. S.J. SARDHAR BASHA who carried out the research under my
supervision. Certified further, that to the best of my knowledge the work
reported herein does not form part of any other thesis or dissertation on
the basis of which a degree or award was conferred on an earlier
occasion on this or any other candidate.

Place : Chennai
Date :

Dr. K. SHANTHI (SUPERVISOR)

Assistant Professor
Department of Chemistry
Anna University
Chennai 600 025

iii

ABSTRACT
In an oil refinery, oil is distilled into several fractions, including
naphtha and gas oil. These fractions must be purified to diminish the contents
of sulfur, nitrogen and metals so that the air-polluting emissions levels of
sulfur and nitrogen oxides are minimized formed when these oil fractions are
burned in cars and trucks. Furthermore, most catalysts used in a refinery for
the processing of oil fractions cannot tolerate sulfur, nitrogen and metals. The
removal of sulfur, nitrogen and metals are performed in so-called
hydrotreating processes in which the feedstock reacts with hydrogen in the
presence of a catalyst.
Over the years, considerable effort has been devoted to the study of
the properties of alumina supported, sulfided cobalt-molybdenum,
nickel-molybdenum and nickel-tungsten catalysts. This has included the
attempts to define the active catalyst species, the role of promoters, the
influence of preparation and activation conditions, etc. The origin of the
exclusive use of alumina can be ascribed to its outstanding textural and
mechanical properties and its relatively low cost. One important factor also is
the ability to regenerate catalytic activity after intensive use under
hydrotreating conditions. Due to the necessity to develop hydrotreating
catalysts with enhanced properties, other supports have been studied
In order to improve the activity and to reduce the severity of
experimental conditions, several approaches have been pursued. One such
approach is to choose proper support for the active components. After the
discovery of mesoporous materials, MCM-41 has received increasing
attention due to its very high surface area and regular pore dimensions.
MCM-41 aluminosilicate favors a high dispersion of the active species while

iv

increasing the accessibility of the large molecules of the gas feed containing
heteroatoms to the catalytic active sites.
The aim of the present investigation was to remove nitrogen using
H-AlMCM-41 as a support for NiO-MoO 3 catalyst. This material has been
used as support for NiO-MoO3 catalysts. H-AlMCM-41 was impregnated
with Mo and Ni precursor salts by sequential impregnation method. The
compositions of the catalysts were chosen as 12, 18, 24 and 30 wt.% of MoO 3
with constant amount of 7 wt.% NiO. These supported catalysts were
characterized using XRD, N2 adsorptiondesorption studies, ICP-AES
elemental analysis, TGA, SEM, FT-Raman spectroscopy, UVVis DRS and
FT-IR spectra of CO adsorption measurements to confirm their crystallinity,
textural properties, coordination environment and fine dispersion of metal
oxides over the support surface. HDN of

o-toluidine (OT) and

cyclohexylamine (CHA) were performed with various metal loadings to

choose the optimum metal loading for these reactions. An activity data show
an enhanced performance with respect to the MoO3 loading. An optimum
metal loading of 24% MoO3 has been chosen to study all the
experiments. The order of activity of the catalyst was 7% NiO 24% MoO 3 >
7% NiO 18% MoO3 > 7% NiO 30% MoO3 > 7% NiO 12% MoO3 /HAlMCM-41 (100)
The NiO-MoO3/H-AlMCM-41 catalysts were prepared by different
procedures like co-impregnation and by sequential impregnation method
(normal order and reverse order). These materials were characterized by
TEM, XRD, N2 adsorption-desorption studies, XPS and FT-IR spectra of CO
adsorption studies. The activity of these catalysts was tested for HDN of OT
and CHA. Reverse order impregnated catalyst (24%MoO 3-7%NiO) shows
higher activity than other catalysts. This may be due to the fine dispersion of
the active metal species and complete reduction of metal oxide to its lower

oxidation state. The activity of the catalysts followed the order 24 wt.% MoO 3
7 wt.% NiO > 7 wt.% NiO 24 wt.% MoO3 > (7 wt.% NiO.24 wt.% MoO3).
The reverse order of impregnation of MoO3 and NiO was chosen for further
studies.
24 wt.% MoO3 and 7 wt.% NiO were sequentionally deposited over
MCM-41 with different Si/Al ratio supported catalysts by reverse order
impregnation. Cetyltrimethylammonium bromide was used as the
structure-directing agent for AlMCM-41 synthesis. The materials were
characterized

by

XRD,

ICP-AES

elemental

analysis,

SEM,

N2 adsorptiondesorption studies, TPD of ammonia using adsorption

techniques, UVVis DRS, MAS NMR and CO adsorption of FT-IR. XRD of
the catalysts clearly show the crystallinity and the phase formation with
respect to NiMoO4, MoO3 and NiO.

27

Al MAS NMR of AlMCM-41 (100)

shows a single peak at 50.85 indicating the presence of aluminium exclusively

in the framework further indicating the complete absence of non-framework
aluminium. Hence, higher Si/Al ratio was observed to be better for
incorporating aluminium exclusively in the framework. The dispersion of
metal oxide over support was calculated by FT-IR of CO adsorption.
HDN of aromatic amines and aliphatic amines like OT and CHA
respectively, were tested over these catalysts. The aliphatic amines show
higher HDN activity than the aromatic amines. Aliphatic amines were found
to readily undergo HDN compared with the aromatic amines.
HDN of OT was also tested over different supported metal catalysts
such as MCM-41, HZSM-5 and -Al2O3 to understand the efficiency level of
MCM-41 supported MoO3-NiO. MCM-41 supported MoO3-NiO catalyst

vi

showed higher activity compared to the other catalysts which might be due to
its high surface area and mild acidity.

ACKNOWLEDGEMENT

It is a great privilege for me to be a student of Dr. K. SHANTHI,

Assistant Professor, Department of Chemistry, Anna University, who has
suggested the problem, offered constructive criticism and encouragement at
every stage of my research work. I pay my gratitude to her, in particular for
her valuable guidance, her meticulous attention to this work and her
exemplary editing of thesis.
My special thanks to Dr. S. NANJUNDAN, Professor and Head,
Department of Chemistry, Anna University for the permission to avail the
laboratory facilities. I wish to place on record my sincere thanks to
Dr. M. PALANICHAMY, Professor in Chemistry, Anna University,
Chennai, for his valuable suggestions rendered during the course of
my work. My sincere thanks to my doctoral committee members
Dr. T. K. VARADHARAJAN and Dr. G. RANGA RAO, IIT, Madras for
their valuable suggestions and encouragement throughout my research career.
I take this opportunity to thank all my seniors, research colleagues
and friends for their fullest cooperation throughout the tenure of this work. I
sincerely thank the non-teaching staff members for their help and support. I
express my deepest appreciation to my parents and brother for their
continuous support and constant encouragement throughout the period of this
work.

vii

S. J. SARDHAR BASHA

viii

TABLE OF CONTENTS

CHAPTER No.

TITLE

PAGE No.

ABSTRACT

iii

LIST OF TABLES

xii

LIST OF FIGURES

xiii

LIST OF SYMBOLS AND ABBREVIATIONS

xvii

INTRODUCTION
1.1

PETROLEUM REFINING IN PETROLEUM

INDUSTRY

1.1.1 Important catalytic processes in

1.2

petroleum refineries

1.1.1.1 Catalytic Cracking

1.1.1.2 Catalytic reforming

1.1.1.3 Hydrocracking

1.1.1.4 Hydrotreating

NITROGEN CONTAINING COMPOUNDS

IN PETROLEUM CRUDE

1.3

CHEMISTRY OF HYDRODENITROGENATION

1.4

9
9

EFFECT OF PARTIAL PRESSURE OF

HYDROGEN ON HYDRODENITROGENATION REACTION

1.5

15

EFFECT OF MoO3 LOADING ON SUPPORT

FOR HYDROTREATING PROCESS

17

ix

CHAPTER No.
1.6

TITLE

PAGE No.

METAL OXIDES AS CATALYSTS FOR

HYDROTREATING PROCESS

1.7

18

METAL CARBIDES AND METAL

NITRIDES AS CATALYSTS FOR HDN

1.8

PHOSPHORUS AS A PROMOTER FOR

HDN CATALYST

1.9

21

FLUORINE AS A PROMOTER FOR

HDN CATALYST

1.10

22

SUPPORT EFFECT ON
HYDROTREATING PROCESS

23

1.10.1 Silica

24

1.10.2 Carbon

24

1.10.3 Oxides as support

26

1.10.3.1 Titania and Zirconia

1.11
2
2.1

20

26

1.10.4 Clays

29

1.10.5 Zeolites as support

31

1.10.6 Mesoporous MCM-41 as support

34

SCOPE OF THE PRESENT STUDY

39

EXPERIMENTAL

41

CHEMICALS
2.2

41

SYNTHESIS OF SUPPORT
2.2.1

42

Synthesis of H-AlMCM-41
support

42

2.2.2

Synthesis of SiMCM-41 support

42

2.2.3

Synthesis of -Al2O3 support

43

2.2.4

Synthesis of HZSM-5 support

44

CHAPTER No.
2.3

TITLE

PAGE No.

PREPARATION OF CATALYSTS

45

2.3.1 Preparation of MCM-41

supported NiO-MoO3 catalyst

45

2.3.2 Preparation of -Al2O3 and HZSM-5

supported NiO-MoO3 catalyst

46

2.4

PRETREATMENT OF CATALYSTS

46

2.5

CHARACTERIZATION OF THE
CATALYSTS

46

2.5.1 X-ray diffraction (XRD)

46

2.5.2 Textural Analysis 47

2.5.3 Thermal Analysis 47
2.5.4 ICP-AES

48

2.5.5 Temperature Programmed

Desorption of Ammonia

48

2.5.6 Nuclear Magnetic Resonance

48

2.5.7 Scanning Electron Microscope

49

2.5.8 FT-Raman Spectroscopy

49

2.5.9 Diffuse Reflectance Spectroscopy

(DRS)

49

2.5.10 Fourier-Transform Infrared

Spectroscopy of CO adsorption

50

2.5.11 Transmission Electron Microscopy

(TEM)

50

2.5.12 X-ray Photoelectron Spectroscopy

(XPS)
2.6

ANALYSIS OF SULFUR

51
51

xi

CHAPTER No.

TITLE
2.7

PAGE No.

FLOW UNIT FOR CATALYST

ACTIVITY MEASUREMENT

2.8
3

53

PRODUCT ANALYSIS

55

RESULTS AND DISCUSSION

57

3.1

EFFECT OF MoO3 LOADING ON

THE HDN ACTIVITY OF NiO-MoO3/
H-AlMCM-41 SUPPORTED CATALYST

57

3.1.1 Characterization

57

3.1.2 Hydrodenitrogenation activity

69

3.1.3 Effect of Reaction time on the

HDN activity

70

3.1.4 Correlation of HDN activity with the

physico-chemical properties of
the catalysts
3.2

75

INFLUENCE OF THE ORDER OF

IMPREGNATION AND METHOD
OF PREPARATION OF NiO-MoO3/HAlMCM-41 CATALYSTS ON THE
HDN ACTIVITY

77

3.2.1 Study of physico-chemical

properties
3.2.2 Hydrodenitrogenation activity

78
92

3.2.3 Correlation of HDN activity with

surface properties of the catalysts

97

3.2.4 Effect of presulfidation on the

HDN activity of the catalyst

99

xii

CHAPTER No.

TITLE
3.3

PAGE No.

EFFECT OF Si/Al RATIO ON HDN

REACTION OVER H-AlMCM-41
SUPPORTED NiO-MoO3 CATALYSTS

101

3.3.1 Characterization

101

3.3.2 Hydrodenitrogenation of OT and

CHA on various AlMCM-41
supported NiO-MoO3 catalysts
3.4

INFLUENCE OF SUPPORT ON
NiO-MoO3 CATALYST FOR HDN

4.

113
116

SUMMARY AND CONCLUSION

118

REFERENCES

123

LIST OF PUBLICATIONS

138

VITAE

140

xiii

LIST OF TABLES
TABLE No.
1.1

TITLE
Consumer products from a petroleum
refinery and their characteristics

1.2

Typical nitrogen compounds present in

petroleum crude

3.1

Nitrogen and Sulfur content present in

different crude

1.3

PAGE No.

10

Textural and structural characteristics of

AlMCM-41 and 7 wt.% NiO-x wt.%MoO3/
H-AlMCM-41

3.2

Textural and structural characteristics of

H-AlMCM-41 and its supported catalysts

3.3

60
82

XPS binding energies (eV) and its

corresponding wt.% of peak area and the
atomic surface concentration
of Mo (CMo) and Ni (CNi)

3.4

Various oxidation states present in NiO-MoO3/

H-AlMCM-41 catalysts

3.5

104

Acidity of H-AlMCM-41 measured by STPD

of ammonia from 353 - 723 K

3.7

85

Textural and structural characteristics of

MCM-41 and its supported catalysts

3.6

84

105

HDN activity and textural characteristics of

different support and supported catalysts

117

xiv

LIST OF FIGURES

FIGURE No.

TITLE

PAGE No.

1.1

Quinoline reaction network

12

1.2

Indole reaction network

13

2.1

Flow unit for catalytic reactions at atmospheric

pressure

3.1

X-ray diffractograms of (a) Protonated

AlMCM-41, (b) Calcined AlMCM-41 and
(c) Uncalcined AlMCM-41

3.2

N2-Adsorption-Desorption isotherm of
AlMCM-41

3.3

59
59

TGA and DTA curves of mesoporous molecular

sieve for as-synthesized sample of
AlMCM-41 (100)

3.4

X-ray diffractograms of 7 wt.% NiO-x wt.% MoO3/

H-AlMCM-41 x = (a) 12, (b) 18 and (c) 24

3.5

63

SEM pictures of (a) AlMCM-41 (100) and

(b) 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41

3.7

63

X-ray diffractogram of 7 wt.% NiO-30 wt.% MoO3/

H-AlMCM-41

3.6

61

65

FT-Raman spectra of 7 wt.% NiO-x wt.%

MoO3/H-AlMCM-41 (a) 18, (b) 24, (c) 12 and
(d) 30

3.8

66

Diffuse reflectance spectra of 7 wt.% NiO-x wt.%

MoO3/H-AlMCM-41 (a) 24, (b) 18, (c) 12 and (d) 30

68

xv

FIGURE No.
3.9

TITLE

PAGE No.

FT-IR spectra of CO adsorbed on reduced

(a) 7 wt.% NiO-18 wt.% MoO3/H-AlMCM-41 and
(b) 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41
catalysts

3.10

Effect of MoO3 loading on the catalytic activity

for the HDN of o-toluidine

3.11

73

Effect of reaction time on the catalytic activity

for the HDN of cyclohexylamine

3.14

72

Effect of reaction time on the catalytic activity

for the HDN of o-toluidine

3.13

71

Effect of MoO3 loading on the catalytic activity

for the HDN of cyclohexylamine

3.12

68

74

TEM images of reduced H-AlMCM-41 supported

catalysts (a) (7 wt.% NiO.24 wt.% MoO3),
(b) 7 wt.% NiO-24 wt.% MoO3 and
(c) 24 wt.% MoO3-7 wt.% NiO

3.15

79

X-ray diffractograms of H-AlMCM-41

supported catalyst (a) (7wt.% NiO.24wt.% MoO3),
(b) 24wt.% MoO3-7wt.% NiO and
(c) 7wt.% NiO-24wt.% MoO3

3.16

XPS spectrum of Mo 3d region for reduced

7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst

3.17

87

XPS spectrum of Mo 3d region for reduced

24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst

3.19

83

XPS spectrum of Mo 3d region for reduced

(7 wt% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst

3.18

81

87

XPS spectrum of Ni 2p region for reduced

7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst

88

xvi

FIGURE No.
3.20

TITLE

PAGE No.

XPS spectrum of Ni 2p region for reduced

(7 wt.% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst

3.21

XPS spectrum of Ni 2p region for reduced

24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst

3.22

88
89

FT-IR spectra of CO adsorbed on reduced

(a) (7wt.% NiO.24wt.% MoO3)/H-AlMCM-41,
(b) 7wt.% NiO-24wt.% MoO3/H-AlMCM-41 and
(c) 24wt.% MoO3-7wt.% NiO/H-AlMCM-41catalyst

3.23

Influence of the impregnation method

on the catalytic activity for the HDN of o-toluidine

3.24

91
93

Influence of the impregnation method

on the catalytic activity for the HDN
of cyclohexylamine

3.25

Effect of reaction time on the catalytic activity

for the HDN of o-toluidine

3.26

96

Effect of pretreatment of NiO-MoO3 catalysts for

the HDN of OT

3.28

95

Effect of reaction time on the catalytic activity

for the HDN of cyclohexylamine

3.27

94

100

X-ray diffractograms of (a) SiMCM-41,

(b) AlMCM-41 (Si/Al = 60) and
(c) AlMCM-41 (Si/Al = 30)

3.29

Effect of pretreatment of NiO-MoO3 catalysts for

the HDN of OT

3.30

103
104

SEM pictures of (a) SiMCM-41,

(b) AlMCM-41 (60) and (c) AlMCM-41 (30)

108

3.31

27

109

3.32

27

109

Al MAS NMR spectrum of AlMCM-41 (30)

Al MAS NMR spectrum of AlMCM-41 (60)

xvii

FIGURE No.

TITLE

3.33

27

3.34

27

Al MAS NMR spectrum of AlMCM-41 (100)

Al MAS NMR spectrum of

111

29

Si MAS NMR spectrum of

24 wt.% MoO3-7 wt.% NiO/SiMCM-41

3.37

110

27

24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 (100)

3.36

110

Al MAS NMR spectrum of

24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 (60)

3.35

PAGE No.

111

Diffuse reflectance spectra of 24 wt.%MoO3

-7 wt.%NiO over different Si/Al ratio support
(a) AlMCM-41 (100), (b) AlMCM-41 (60) and
(c) SiMCM-41

3.38

112

FT-IR spectra of CO adsorbed on reduced

24 wt.% MoO3-7 wt.% NiO over different
Si/Al ratio support (a) AlMCM-41 (100),
(b) AlMCM-41 (60), (c) SiMCM-41 and
(d) AlMCM-41 (30)

3.39

114

Effect of Si/Al ratio on the catalytic activity for

the HDN of o-toluidine and Cyclohexylamine

115

xviii

LIST OF SYMBOLS AND ABBREVIATIONS

Angstron unit

a.u.

Arbitrary unit

BE

Binding energy

BET

Brunauer, Emmett and Teller

cm3/g

Cubic centimeter per gram

CTAB

Cetyltrimethylammonium bromide

FT-IR

Fourier transform infrared spectroscopy

Gram

GC

Gas chromatography

Hour

HDM

Hydrodemetallization

HDN

Hydrodenitrogenation

HDO

Hydrodeoxygenation

HDS

Hydrodesulfurisation

HT

Hydrotreating

ICP-AES

Inductive coupled plasma-atomic emission

spectroscopy

Kelvin

LHSV

Liquid hour space velocity

m2/g

Square metre per gram

MAS

Magic angle spinning

MCM

Mobil corporation material

min

Minute

ml

Millilitre

nm

Nanometre

NMR

Nuclear magnetic resonance

Degree celsius

xix

Second

SEM

Scanning electron microscope

Temperature

TEM

Transmission electron microscope

TGA

Thermogravimetry analysis

TOS

Time on stream

USY

Ultra stable

UV-Vis DRS

UV-Visible Diffuse reflectance

spectroscopy

Wt. %

Weight percentage

XPS

X-ray photoelectron spectroscopy

XRD

X-ray diffraction

Gamma

Theta