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

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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 Date :

Dr. K. SHANTHI (SUPERVISOR) Assistant Professor Department of Chemistry Anna University Chennai 600 025

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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

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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-MoO3 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 MoO 3 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.
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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

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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

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TABLE OF CONTENTS

CHAPTER No. ABSTRACT

TITLE

PAGE No. iii xii xiii xvii 1 1 3 3 4 5 6 9 9

LIST OF TABLES LIST OF FIGURES LIST OF SYMBOLS AND ABBREVIATIONS 1 INTRODUCTION 1.1 PETROLEUM REFINING IN PETROLEUM INDUSTRY 1.1.1 Important catalytic processes in petroleum refineries 1.1.1.1 Catalytic Cracking 1.1.1.2 Catalytic reforming 1.1.1.3 Hydrocracking 1.1.1.4 Hydrotreating 1.2 1.3 1.4 NITROGEN CONTAINING COMPOUNDS IN PETROLEUM CRUDE CHEMISTRY OF HYDRODENITROGENATION EFFECT OF PARTIAL PRESSURE OF HYDROGEN ON HYDRODENITROGENATION REACTION 1.5 EFFECT OF MoO3 LOADING ON SUPPORT FOR HYDROTREATING PROCESS

15 17

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CHAPTER No. 1.6 1.7 1.8 1.9 1.10

TITLE METAL OXIDES AS CATALYSTS FOR HYDROTREATING PROCESS METAL CARBIDES AND METAL NITRIDES AS CATALYSTS FOR HDN PHOSPHORUS AS A PROMOTER FOR HDN CATALYST FLUORINE AS A PROMOTER FOR HDN CATALYST SUPPORT EFFECT ON HYDROTREATING PROCESS 1.10.1 Silica 1.10.2 Carbon 1.10.3 Oxides as support 1.10.3.1 Titania and Zirconia 1.10.4 Clays 1.10.5 Zeolites as support 1.10.6 Mesoporous MCM-41 as support

PAGE No.

18 20 21 22 23 24 24 26 26 29 31 34 39 41 41 42 42 42 43 44

1.11 2 2.1

SCOPE OF THE PRESENT STUDY EXPERIMENTAL CHEMICALS 2.2 2.2.1 2.2.2 2.2.3 2.2.4 SYNTHESIS OF SUPPORT Synthesis of H-AlMCM-41 support Synthesis of SiMCM-41 support Synthesis of -Al2O3 support Synthesis of HZSM-5 support

CHAPTER No. 2.3

TITLE PREPARATION OF CATALYSTS 2.3.1 Preparation of MCM-41 supported NiO-MoO3 catalyst

PAGE No. 45 45 46 46 46 46

2.3.2 Preparation of -Al2O3 and HZSM-5 supported NiO-MoO3 catalyst 2.4 2.5 PRETREATMENT OF CATALYSTS CHARACTERIZATION OF THE CATALYSTS 2.5.1 X-ray diffraction (XRD) 2.5.2 Textural Analysis 47 2.5.3 Thermal Analysis 47 2.5.4 ICP-AES 48 48 48 49 49 49 50 50 51 51 2.5.5 Temperature Programmed Desorption of Ammonia 2.5.6 Nuclear Magnetic Resonance 2.5.7 Scanning Electron Microscope 2.5.8 FT-Raman Spectroscopy 2.5.9 Diffuse Reflectance Spectroscopy (DRS) 2.5.10 Fourier-Transform Infrared Spectroscopy of CO adsorption 2.5.11 Transmission Electron Microscopy (TEM) 2.5.12 X-ray Photoelectron Spectroscopy (XPS) 2.6 ANALYSIS OF SULFUR

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CHAPTER No. 2.7 2.8 3

TITLE FLOW UNIT FOR CATALYST ACTIVITY MEASUREMENT PRODUCT ANALYSIS RESULTS AND DISCUSSION 3.1 EFFECT OF MoO3 LOADING ON

PAGE No.

53 55 57

THE HDN ACTIVITY OF NiO-MoO3/ H-AlMCM-41 SUPPORTED CATALYST 3.1.1 Characterization 3.1.2 Hydrodenitrogenation activity 3.1.3 Effect of Reaction time on the HDN activity 3.1.4 Correlation of HDN activity with the physico-chemical properties of the catalysts 3.2 INFLUENCE OF THE ORDER OF IMPREGNATION AND METHOD OF PREPARATION OF NiO-MoO3/HAlMCM-41 CATALYSTS ON THE HDN ACTIVITY 3.2.1 Study of physico-chemical properties 3.2.2 Hydrodenitrogenation activity 3.2.3 Correlation of HDN activity with surface properties of the catalysts 3.2.4 Effect of presulfidation on the HDN activity of the catalyst 99 97 78 92 77 75 70 57 57 69

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CHAPTER No. 3.3

TITLE EFFECT OF Si/Al RATIO ON HDN REACTION OVER H-AlMCM-41

PAGE No.

SUPPORTED NiO-MoO3 CATALYSTS 3.3.1 Characterization 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. SUMMARY AND CONCLUSION REFERENCES LIST OF PUBLICATIONS VITAE

101 101

113 116 118 123 138 140

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LIST OF TABLES
TABLE No. 1.1 1.2 1.3 3.1 TITLE Consumer products from a petroleum refinery and their characteristics Nitrogen and Sulfur content present in different crude Typical nitrogen compounds present in
petroleum crude 10

PAGE No.

3 8

Textural and structural characteristics of AlMCM-41 and 7 wt.% NiO-x wt.%MoO3/ H-AlMCM-41 60 82

3.2 3.3

Textural and structural characteristics of H-AlMCM-41 and its supported catalysts XPS binding energies (eV) and its corresponding wt.% of peak area and the atomic surface concentration of Mo (CMo) and Ni (CNi) 84 85 104
105

3.4 3.5 3.6 3.7

Various oxidation states present in NiO-MoO3/ H-AlMCM-41 catalysts Textural and structural characteristics of MCM-41 and its supported catalysts Acidity of H-AlMCM-41 measured by STPD
of ammonia from 353 - 723 K

HDN activity and textural characteristics of different support and supported catalysts 117

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LIST OF FIGURES

FIGURE No. 1.1 1.2 2.1 3.1

TITLE

PAGE No. 12 13 54

Quinoline reaction network Indole reaction network Flow unit for catalytic reactions at atmospheric pressure X-ray diffractograms of (a) Protonated AlMCM-41, (b) Calcined AlMCM-41 and (c) Uncalcined AlMCM-41

59 59

3.2 3.3

N2-Adsorption-Desorption isotherm of AlMCM-41 TGA and DTA curves of mesoporous molecular sieve for as-synthesized sample of AlMCM-41 (100) 61 63 63 65

3.4 3.5 3.6 3.7

X-ray diffractograms of 7 wt.% NiO-x wt.% MoO3/ H-AlMCM-41 x = (a) 12, (b) 18 and (c) 24 X-ray diffractogram of 7 wt.% NiO-30 wt.% MoO3/ H-AlMCM-41 SEM pictures of (a) AlMCM-41 (100) and (b) 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 FT-Raman spectra of 7 wt.% NiO-x wt.% MoO3/H-AlMCM-41 (a) 18, (b) 24, (c) 12 and (d) 30 66 68

3.8

Diffuse reflectance spectra of 7 wt.% NiO-x wt.% MoO3/H-AlMCM-41 (a) 24, (b) 18, (c) 12 and (d) 30

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FIGURE No. 3.9

TITLE FT-IR spectra of CO adsorbed on reduced

PAGE No.

(a) 7 wt.% NiO-18 wt.% MoO3/H-AlMCM-41 and (b) 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalysts 3.10 3.11 3.12 3.13 3.14 Effect of MoO3 loading on the catalytic activity for the HDN of o-toluidine Effect of MoO3 loading on the catalytic activity for the HDN of cyclohexylamine Effect of reaction time on the catalytic activity for the HDN of o-toluidine Effect of reaction time on the catalytic activity for the HDN of cyclohexylamine 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 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 3.17 3.18 3.19 XPS spectrum of Mo 3d region for reduced 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst XPS spectrum of Mo 3d region for reduced (7 wt% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst XPS spectrum of Mo 3d region for reduced 24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst XPS spectrum of Ni 2p region for reduced 7 wt.% NiO-24 wt.% MoO3/H-AlMCM-41 catalyst 88 87 87 83 81 79 74 73 72 71 68

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FIGURE No. 3.20 3.21 3.22

TITLE XPS spectrum of Ni 2p region for reduced

PAGE No.

(7 wt.% NiO.24 wt.% MoO3)/H-AlMCM-41 catalyst XPS spectrum of Ni 2p region for reduced 24 wt.% MoO3-7 wt.% NiO/H-AlMCM-41 catalyst 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 3.24 Influence of the impregnation method on the catalytic activity for the HDN of o-toluidine Influence of the impregnation method on the catalytic activity for the HDN of cyclohexylamine 3.25 3.26 3.27 3.28 Effect of reaction time on the catalytic activity for the HDN of o-toluidine Effect of reaction time on the catalytic activity for the HDN of cyclohexylamine Effect of pretreatment of NiO-MoO3 catalysts for the HDN of OT X-ray diffractograms of (a) SiMCM-41, (b) AlMCM-41 (Si/Al = 60) and (c) AlMCM-41 (Si/Al = 30) 3.29 3.30 3.31 3.32 Effect of pretreatment of NiO-MoO3 catalysts for the HDN of OT SEM pictures of (a) SiMCM-41, (b) AlMCM-41 (60) and (c) AlMCM-41 (30)
27 27

88 89

91 93

94 95 96 100

103 104 108 109 109

Al MAS NMR spectrum of AlMCM-41 (30) Al MAS NMR spectrum of AlMCM-41 (60)

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FIGURE No. 3.33 3.34 3.35 3.36 3.37

27 27

TITLE Al MAS NMR spectrum of AlMCM-41 (100) Al MAS NMR spectrum of

PAGE No. 110 110 111 111

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

27

Al MAS NMR spectrum of Si MAS NMR spectrum of

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

29

24 wt.% MoO3-7 wt.% NiO/SiMCM-41 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 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 Effect of Si/Al ratio on the catalytic activity for the HDN of o-toluidine and Cyclohexylamine

112

114 115

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LIST OF SYMBOLS AND ABBREVIATIONS

a.u. BE BET cm3/g CTAB FT-IR g GC h HDM HDN HDO HDS HT ICP-AES K LHSV m2/g MAS MCM min ml nm NMR C Angstron unit Arbitrary unit Binding energy Brunauer, Emmett and Teller Cubic centimeter per gram Cetyltrimethylammonium bromide Fourier transform infrared spectroscopy Gram Gas chromatography Hour Hydrodemetallization Hydrodenitrogenation Hydrodeoxygenation Hydrodesulfurisation Hydrotreating Inductive coupled plasma-atomic emission spectroscopy Kelvin Liquid hour space velocity Square metre per gram Magic angle spinning Mobil corporation material Minute Millilitre Nanometre Nuclear magnetic resonance Degree celsius

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s SEM T TEM TGA TOS USY UV-Vis DRS Wt. % XPS XRD

Second Scanning electron microscope Temperature Transmission electron microscope Thermogravimetry analysis Time on stream Ultra stable UV-Visible Diffuse reflectance spectroscopy Weight percentage X-ray photoelectron spectroscopy X-ray diffraction Gamma Theta