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
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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 Dr. K. SHANTHI (SUPERVISOR)

Assistant Professor
Date : 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.
 iv

MCM-41 aluminosilicate favors a high dispersion of the active species while

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 adsorption–desorption studies, ICP-AES
elemental analysis, TGA, SEM, FT-Raman spectroscopy, UV–Vis 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 /H-
AlMCM-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
 v

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 adsorption–desorption studies, TPD of ammonia using adsorption
techniques, UV–Vis DRS, MAS NMR and CO adsorption of FT-IR. XRD of
the catalysts clearly show the crystallinity and the phase formation with
27
respect to NiMoO4, MoO3 and NiO. 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 γ-Al2O3 to understand the efficiency level of
MCM-41 supported MoO3-NiO. MCM-41 supported MoO3-NiO catalyst
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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.
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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

1 INTRODUCTION 1
1.1 PETROLEUM REFINING IN PETROLEUM
INDUSTRY 1
1.1.1 Important catalytic processes in
petroleum refineries 3
1.1.1.1 Catalytic Cracking 3
1.1.1.2 Catalytic reforming 4
1.1.1.3 Hydrocracking 5
1.1.1.4 Hydrotreating 6
1.2 NITROGEN CONTAINING COMPOUNDS
IN PETROLEUM CRUDE 9
1.3 CHEMISTRY OF HYDRODENITRO-
GENATION 9
1.4 EFFECT OF PARTIAL PRESSURE OF
HYDROGEN ON HYDRODENITRO-
GENATION REACTION 15
1.5 EFFECT OF MoO3 LOADING ON SUPPORT
FOR HYDROTREATING PROCESS 17
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CHAPTER No. TITLE PAGE No.

1.6 METAL OXIDES AS CATALYSTS FOR

HYDROTREATING PROCESS 18
1.7 METAL CARBIDES AND METAL
NITRIDES AS CATALYSTS FOR HDN 20
1.8 PHOSPHORUS AS A PROMOTER FOR
HDN CATALYST 21
1.9 FLUORINE AS A PROMOTER FOR
HDN CATALYST 22
1.10 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 26
1.10.4 Clays 29
1.10.5 Zeolites as support 31
1.10.6 Mesoporous MCM-41 as support 34
1.11 SCOPE OF THE PRESENT STUDY 39

2 EXPERIMENTAL 41
2.1 CHEMICALS 41
2.2 SYNTHESIS OF SUPPORT 42
2.2.1 Synthesis of H-AlMCM-41
support 42
2.2.2 Synthesis of SiMCM-41 support 42
2.2.3 Synthesis of γ-Al2O3 support 43
2.2.4 Synthesis of HZSM-5 support 44
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CHAPTER No. TITLE PAGE No.

2.3 PREPARATION OF CATALYSTS 45

2.3.1 Preparation of MCM-41
supported NiO-MoO3 catalyst 45
2.3.2 Preparation of γ-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) 51
2.6 ANALYSIS OF SULFUR 51
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CHAPTER No. TITLE PAGE No.

2.7 FLOW UNIT FOR CATALYST

ACTIVITY MEASUREMENT 53
2.8 PRODUCT ANALYSIS 55

3 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 75
3.2 INFLUENCE OF THE ORDER OF
IMPREGNATION AND METHOD
OF PREPARATION OF NiO-MoO3/H-
AlMCM-41 CATALYSTS ON THE
HDN ACTIVITY 77
3.2.1 Study of physico-chemical
properties 78
3.2.2 Hydrodenitrogenation activity 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
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CHAPTER No. TITLE PAGE No.

3.3 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 113
3.4 INFLUENCE OF SUPPORT ON
NiO-MoO3 CATALYST FOR HDN 116

4. SUMMARY AND CONCLUSION 118

REFERENCES 123

LIST OF PUBLICATIONS 138

VITAE 140
 xiii

LIST OF TABLES

TABLE No. TITLE PAGE No.

1.1 Consumer products from a petroleum

refinery and their characteristics 3
1.2 Nitrogen and Sulfur content present in
different crude 8
1.3 Typical nitrogen compounds present in
petroleum crude 10
3.1 Textural and structural characteristics of
AlMCM-41 and 7 wt.% NiO-x wt.%MoO3/
H-AlMCM-41 60
3.2 Textural and structural characteristics of
H-AlMCM-41 and its supported catalysts 82
3.3 XPS binding energies (eV) and its
corresponding wt.% of peak area and the
atomic surface concentration
of Mo (CMo) and Ni (CNi) 84
3.4 Various oxidation states present in NiO-MoO3/
H-AlMCM-41 catalysts 85
3.5 Textural and structural characteristics of
MCM-41 and its supported catalysts 104
3.6 Acidity of H-AlMCM-41 measured by STPD
of ammonia from 353 - 723 K 105
3.7 HDN activity and textural characteristics of
different support and supported catalysts 117
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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 54
3.1 X-ray diffractograms of (a) Protonated
AlMCM-41, (b) Calcined AlMCM-41 and
(c) Uncalcined AlMCM-41 59
3.2 N2-Adsorption-Desorption isotherm of
AlMCM-41 59
3.3 TGA and DTA curves of mesoporous molecular
sieve for as-synthesized sample of
AlMCM-41 (100) 61
3.4 X-ray diffractograms of 7 wt.% NiO-x wt.% MoO3/
H-AlMCM-41 x = (a) 12, (b) 18 and (c) 24 63
3.5 X-ray diffractogram of 7 wt.% NiO-30 wt.% MoO3/
H-AlMCM-41 63
3.6 SEM pictures of (a) AlMCM-41 (100) and
(b) 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 65
3.7 FT-Raman spectra of 7 wt.% NiO-x wt.%
MoO3/H-AlMCM-41 (a) 18, (b) 24, (c) 12 and
(d) 30 66
3.8 Diffuse reflectance spectra of 7 wt.% NiO-x wt.%
MoO3/H-AlMCM-41 (a) 24, (b) 18, (c) 12 and (d) 30 68
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FIGURE No. TITLE PAGE No.

3.9 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 68
3.10 Effect of MoO3 loading on the catalytic activity
for the HDN of o-toluidine 71
3.11 Effect of MoO3 loading on the catalytic activity
for the HDN of cyclohexylamine 72
3.12 Effect of reaction time on the catalytic activity
for the HDN of o-toluidine 73
3.13 Effect of reaction time on the catalytic activity
for the HDN of cyclohexylamine 74
3.14 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 79
3.15 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 81
3.16 XPS spectrum of Mo 3d region for reduced
7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst 83
3.17 XPS spectrum of Mo 3d region for reduced
(7 wt% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst 87
3.18 XPS spectrum of Mo 3d region for reduced
24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst 87
3.19 XPS spectrum of Ni 2p region for reduced
7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst 88
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FIGURE No. TITLE PAGE No.

3.20 XPS spectrum of Ni 2p region for reduced

(7 wt.% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst 88
3.21 XPS spectrum of Ni 2p region for reduced
24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst 89
3.22 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 91
3.23 Influence of the impregnation method
on the catalytic activity for the HDN of o-toluidine 93
3.24 Influence of the impregnation method
on the catalytic activity for the HDN
of cyclohexylamine 94
3.25 Effect of reaction time on the catalytic activity
for the HDN of o-toluidine 95
3.26 Effect of reaction time on the catalytic activity
for the HDN of cyclohexylamine 96
3.27 Effect of pretreatment of NiO-MoO3 catalysts for
the HDN of OT 100
3.28 X-ray diffractograms of (a) SiMCM-41,
(b) AlMCM-41 (Si/Al = 60) and
(c) AlMCM-41 (Si/Al = 30) 103
3.29 Effect of pretreatment of NiO-MoO3 catalysts for
the HDN of OT 104
3.30 SEM pictures of (a) SiMCM-41,
(b) AlMCM-41 (60) and (c) AlMCM-41 (30) 108
27
3.31 Al MAS NMR spectrum of AlMCM-41 (30) 109
27
3.32 Al MAS NMR spectrum of AlMCM-41 (60) 109
 xvii

FIGURE No. TITLE PAGE No.

27
3.33 Al MAS NMR spectrum of AlMCM-41 (100) 110
27
3.34 Al MAS NMR spectrum of
24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 (60) 110
27
3.35 Al MAS NMR spectrum of
24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 (100) 111
29
3.36 Si MAS NMR spectrum of
24 wt.% MoO3-7 wt.% NiO/SiMCM-41 111
3.37 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-41 112
3.38 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) 114
3.39 Effect of Si/Al ratio on the catalytic activity for
the HDN of o-toluidine and Cyclohexylamine 115
 xviii

LIST OF SYMBOLS AND ABBREVIATIONS

Å - 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
g - Gram
GC - Gas chromatography
h - Hour
HDM - Hydrodemetallization
HDN - Hydrodenitrogenation
HDO - Hydrodeoxygenation
HDS - Hydrodesulfurisation
HT - Hydrotreating
ICP-AES - Inductive coupled plasma-atomic emission
spectroscopy
K - 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
ºC - Degree celsius
 xix

s - Second
SEM - Scanning electron microscope
T - 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
γ - Gamma
θ - Theta