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The preparation, characterization and catalytic activity of a new sold acid catalyst system

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Title:
The preparation, characterization and catalytic activity of a new sold acid catalyst system
Creator:
Getty, Edward E., 1962-
Publication Date:
Language:
English
Physical Description:
xv, 203 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Aluminum ( jstor )
Carbon ( jstor )
Catalysts ( jstor )
Chlorides ( jstor )
Oxides ( jstor )
Pyridines ( jstor )
Silica gel ( jstor )
Silicon ( jstor )
Solvents ( jstor )
Tetrachlorides ( jstor )
Aluminum chloride ( lcsh )
Catalysis ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Heterogeneous catalysis ( lcsh )
Superacids ( lcsh )
City of Gainesville ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Edward E. Getty.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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024800784 ( ALEPH )
20076968 ( OCLC )
AFM0849 ( NOTIS )
AA00004802_00001 ( sobekcm )

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'TE PREPARATION, CHARACTERIZATION AND
CATALYTIC ACTIVITY OF A NEW SOLID ACID CATALYST SYSTEM















By

EDEARD E. GETTY


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DECGEE OF
DOCTOR OF PHIIDSOPHY

UNIVERSITY OF FIORIDA

1988

3'OF F LIBRAR!F




TOE PREPARATION, CHARACTERIZATION AND
CATALYTIC ACTIVITY OF A NEW SOLID ACID CATALYST SYSTEM
By
EDWARD E. GETTY
A DISSERTATION PRESENTED TO TOE GRADUATE SCHOOL
OF TOE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF TOE REQUIREMENTS FOR TOE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988
U OF F LIBRARIES


To my parents


ACKNOWLEDGEMEfTTS
I would like to express my gratitude to Professor Russell S.
Drago for his support and encouragement over the past four years.
Doc made my years in graduate school very enjoyable both in the lab
and on the tennis court. I would also like to thank Ruth Drago for
making Florida seem like a heme.
I would like to thank all the members of the Drago group for
their support over the last four your years. I would especially
like to thank Mark Barnes, Jerry Grnewald, Larry Chamusco, and Ngai
Wong for their friendship and help. A special thank you goes to
Alan Goldstein for his comradeship and support.
I am deeply indebted to my wife, Cindy, for all her love and
devotion during our time in graduate school. She has shown me that
there is more to life than work. I will love her always.
iii


TABLE OF CONTENTS
Page
ACKNOWIEDGEMENIS iii
TABLE OF OONTENTS iv
LIST OF TABLES viii
LIST OF FIGURES X
ABSTRACT xiv
CHAPTERS
I. INTRODUCTION 1
II. REACTION OF HYDROCARBONS 3
2.1 Background 3
2.2 Experimental 9
Reagents 9
Instrumentation 11
Fixed Bed Flew Reactor 13
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using Carbon Tetrachloride as
a Solvent 14
Preparation of an Alumina Catalyst Doped with
Aluminum Chloride Using Carbon Tetrachloride as
a Solvent 15
Preparation of a High-Silica Zeolite Doped with
Aluminum Chloride Using Carbon Tetrachloride as
a Solvent 18
Preparation of a Y-Zeolite Catalyst Doped with
Aluminum Chloride Using Carbon Tetrachloride as
a Solvent 18
Preparation of a Boron Oxide Catalyst Doped with
Aluminum Chloride Using Carbon Tetrachloride as
a Solvent 19
iv


Preparation of a Titanium Dioxide Catalyst Doped
with Aluminum Chloride Using Carbon
Tetrachloride as a Solvent 20
Preparation of a Magnesium Oxide Catalyst Doped
with Aluminum Chloride Using Carbon
Tetrachloride as a Solvent 20
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using Chloroform as a Solvent. 21
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using Methylene Chloride as a
Solvent 22
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using 1,2-Dichloroethane as a
Solvent 22
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using n-Hexane as a Solvent... 23
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using Cyclohexane as a Solvent 24
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride Using Benzene as a Solvent.... 24
Preparation of a Silica Gel Catalyst Doped with
Aluminum Chloride by Vapor Deposition 25
Preparation of a Palladium (II) Chloride-Aluminum
Chloride Doped Catalyst Using Carbon
Tetrachloride as a Solvent 25
Preparation of a Rhodium (III) Chloride-Aluminum
Chloride Doped Catalyst Using Carbon
Tetrachloride as a Solvent 26
Procedure for the Adsorption of Pyridine onto
Supports and Solid Acid Catalysts for the
Characterization of Acid Sites 26
Procedure for the Spin Trapping of Radicals on
Solid Acid Catalysts Using CMPO 27
2.3 Results and Discussion 28
Preparation of a New Solid Acid Catalyst 28
v


33
Characterization of the New Solid Acid Catalysts
by the Infrared Spectroscopy of Adsorbed
Pyridine
Characterization of a New Solid Acid Catalyst by
27A1 and 29Si Solid-State Magic Angle Spinning
(MAS) FT NMR Spectroscopy 44
Characterization of the Radical on the Catalyst
Surface 59
Titration of Strong Acid Sites with Pyridine 64
Catalytic Cracking of Hydrocarbons by a New Solid
Catalyst System 65
Reaction of an Aluminum Chloride Treated Silica
Gel with Various Straight Chained Hydrocarbons
in a Fixed Bed Flew Reactor 65
Reactions of Various Aluminum Chloride
Functionalized Inorganic Oxides with
Hydrocarbons in a Batch Reactor 90
Reactions of Hydrocarbon Substrates with an
Improved Solid Acid Catalyst in a Syringe Pump
Flew Reactor 113
Other Acid Catalyzed Reactions Involving
Hydrocarbons and Solid Acid Catalysts 122
2.4 Summary 134
III. REACTION OF CHLORINATED HYDROCARBONS 137
3.1 Background 137
3.2 Experimental 140
Reagents 140
Preparation of a Palladium (II) Chloride-Aluminum
Chloride Doped Catalyst Using Carbon
Tetrachloride as a Solvent 142
Preparation of a Rhodium (III) Chloride-Aluminum
Chloride Doped Silica Gel Catalyst Using Carbon
Tetrachloride as a Solvent 143
vi


143
Preparation of a Dipotassium Palladium (II)
Chloride-Aluminum Chloride Doped Catalyst Using
Carton Tetrachloride as a Solvent
Preparation of a Ruthenium (III) Chloride Doped
Catalyst Using Carton Tetrachloride as a Solvent 144
Preparation of a Copper (II) Chloride-Aluminum
Chloride Doped Catalyst Using Carton
Tetrachloride as a Solvent 144
Preparation of a Cobalt (II) Chloride-Aluminum
Chloride Doped Catalyst Using Carbon
Tetrachloride as a Solvent 145
Preparation of a Iron (III) Chloride-Aluminum
Chloride Doped Catalyst Using Carbon
Tetrachloride as a Solvent 146
3.3 Results and Discussion 146
Hydrogenation of C-Cl Bonds 146
Hydrodechlorination of Carbon Tetrachloride at
High Conversion Rates 178
Homogeneous Hydrodechlorination of Carbon
Tetrachloride 181
3.4 Summary 189
IV. CONCLUSION 193
REFERENCES 197
BIOGRAFKECAL SKETCH 203
vii


TART F
NUMBER
LIST OF TARTES
Title Page
2-1 Infrared Shift Data for Pyridine Adsorbed onto
A1C12-X Catalysts 39
2-2 Products Obtained by Cracking Isobutane 89
2-3 Activities for Different AlCl2-Functionalized
Supports 93
2-4 Activities for AlCl2-Si02 Catalysts Prepared in
Different Solvents 96
2-5 Product Distribution for Catalysts with Varying
Percents of Aluminum Chloride on Silicon
Dioxide 99
2-6 Activities for Catalysts with Varying Percents of
Aluminum Chloride on Silicon Dioxide 100
2-7 Product Distribution for Catalysts with Varying
Surface Areas Using 50 wt% Aluminum Chloride
on Silicon Dioxide 102
2-8 Activities for Catalysts with Varying Surface
Areas Using 50 wt% Aluminum Chloride on
Silicon Dioxide 102
2-9 Product Distribution for the 50 wt% Aluminum
Chloride on Silicon Dioxide Under Various
Experimental Conditions 106
2-10 Activities for the Catalyst with 50 wt% Aluminum
Chloride on Silicon Dioxide under Various
Experimental Conditions 107
2-11 Activities for AlCl2-Si02 Catalyst in Different
Solvents and Different Temperatures 108
2-12 Product Distributions for AlCl2-Si02 Catalyst in
Different Solvents and Different Temperatures... 109
2-13 Activities for AlCl2-Si02 Catalyst at Different
Feed Percents in Carbon Tetrachloride at 100 C
and 25 psig H2 Ill
2-14 Product Distributions for AlCl2-Si02 Catalyst at
Different Feed Percents in Carbon Tetrachloride
at 100 C and 25 psig H2 112
viii


LIST OF TABLES
(Cont'd)
Table
Number Page
3-1 Product Distribution for Bd(II)AlCl2-Si02 Catalyst
at 90 C with H2 and CC14 148
3-2 Product Distribution for a 3% Palladium-on-
Charcoal Catalyst at 90 C with H2 and CC14 149
ix


LIST OF FIGURES
Figure
Number Figure Title Page
2-1 The Bending Modes for Pyridine 7
2-2 An EFR Spectrum of a Heterogeneous Acid Catalyst
Before Ccrplete Reaction 16
2-3 An EFR Spectrum of a Heterogeneous Acid Catalyst
After Ccrplete Reaction 17
2-4 Infrared Spectrum of Si02 Dried at 200 C 30
2-5 Infrared Spectrum of SiO^ After Pyridine
Adsorption and Evacuation at Room Temperature... 31
2-6 Infrared Spectrum of SiO^ After Pyridine
Adsorption and Evacuation at 150 C 32
2-7 Infrared Spectrum of AlCl2-Si02 Dried at 200C.... 34
2-8 Infrared Spectrum of AlCl2-Si02 After Pyridine
Adsorption and Evacuation at Rocm Temperature... 36
2-9 Infrared Spectrum of AlCl2-Si02 After Pyridine
Adsorption and Evacuation at 150 C 37
2-10 Infrared Spectrum of AlCl2-Si02 After Pyridine
Adsorption and Evacuation at 300C 38
2-11 An 27A1 Solid-State NMR of an AlCl2-Si02 Catalyst
F>repared in the Fresence of H20 46
2-12 A 29si Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared in the Presence of H20 47
2-13 An 27A1 Solid-State NMR of an Active AlCl2-Si02
Catalyst Prepared in the Absence of H20 49
2-14 An 27A1 Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared with a 690 m^/gram Surface Area Silica
Gel 51
2-15 A 29Si Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared with a 690 m2/gram Surface Area Silica
Gel 52
2-16 An 27A1 Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared with 100 wt% of Aluminum Chloride 54
x


LIST OF FIGURES
(Cont'd)
Figure
Number Figure Title Page
2-17 A 29Si Solid-State NMR of an AlC^-SiC^ Catalyst
Prepared with 100 wt% of Aluminum Chloride 55
2-18 An 27A1 Solid-State NMR of an AlCl2-Si02 Catalyst
After Reaction with n-Pentane 57
2-19 A 29Si Solid-State NMR of an AlCl2-Si02 Catalyst
After Reaction with n-Pentane 58
2-20 Radical on AlCl2-Si02 Spin Trapped Using CMPO
in Toluene 60
2-21 EFR Simulation of Radical on AlCl2-Si02 61
2-22 GC Chromatogram from the Reaction of n-Pentane
with a Solid Acid Catalyst at Fast Flow Rates... 67
2-23 GC Chromatogram from the Reaction of n-Pentane
with a Solid Acid Catalyst at Slew Flew Rates... 68
2-24 Activity Curves for the Reaction of n-Pentane with
a Solid Acid Catalyst at 175 C 69
2-25 GC Chromatogram from the Reaction of n-Heptane
with a Solid Acid Catalyst at 175 C 72
2-26 Mass Intensity Report for Propane 73
2-27 Mass Intensity Report for Isobutane 74
2-28 Mass Intensity Report for n-Butane 75
2-29 Mass Intensity Report for Isopentane 76
2-30 Mass Intensity Report for n-Pentane 77
2-31 Activity Curves for the Reaction of n-Heptane with
a Solid Acid Catalyst at 175 C 78
2-32 A Simplified Scheme for the Cracking of n-Heptane. 80
2-33 A Mechanism for the Catalytic Cracking of
Hydrocarbons in the Presence of CC14 85
2-34 GC Chromatogram from the Cracking of Resid with a
Solid Acid Catalyst at 175C 91
xi


LIST OF FIGURES
(Cont'd)
Figure
Number Figure Title Page
2-35 Major Products from the Reaction of n-Hexadecane
with a Solid Acid Catalyst at 175C 116
2-36 GC-FITR Chromatogram of the Product Stream from
the Reaction of a Fd(II)Cl2AlCl2-Si02 Catalyst
with n-Hexadecane at 175C 118
2-37 Major Products from the Reaction of n-Hexadecane
with a Pd(II)CI2AICI2-SO2 Catalyst at 175C.... 119
2-38 Comparison of the A1C12- and Pd(II)Cl2AlCl2-Si02
Catalysts 120
2-39 Infrared Spectrum of Purified Neat 1-Hexene 124
2-40 Infrared Spectrum of Polymerized 1-Hexene 125
2-41 Pregas Sample for the Alkylative Condensation of
Methane by a Solid Acid Catalyst 129
2-42 Post Gas Sample for the Alkylative Condensation of
Methane by a Solid Acid Catalyst at 175 C 130
2-43 Post Gas Sample for the Cracking of n-Pentane
at 175 C 132
3-1 Plot of Activity vs Time for the Reaction of
Pd (11) Cl 2A1C12 -S i02 Catalyst with CC14 and
H2 at 90C 152
3-2 Comparison of the Product Distributions for the
Reaction of Various Catalysts with CC14 at 100 C 159
3-3 GC-FITR Chromatogram of the Product Stream from
the Reaction of a Pd(II)Cl2AlCl2-Si02 Catalyst
with 1,2-Dichloroethane at 175C 161
3-4 Infrared Spectrum of Vinyl Chloride with EPA Vapor
Ihase Library Best Matches 163
3-5 Product Distribution from the Reaction of 1,2-
Dichloroethane with Pd(II)Cl2AlCl2-Si02
Catalyst at 100C and a Flew Rate of lmI/2.4 sec 164
xii


LIST OF FIGURES
(Cont'd)
Figure
Number Figure Title Page
3-6 Product Distribution from the Reaction of 1,2-
Dichloroethane with Pd(II) CI2AICI2-SO2
{Type II} Catalyst at 100C and Various Addition
Times 165
3-7 Product Distribution from the Reaction of 1,2-
Dichloroethane with Pd(II)Cl2AlCl2Si02
{Type II} Catalyst at Various Temperatures 166
3-8 Product Distribution from the Reaction of 1,2-
Dichloroethane with Rh(III)Cl3AlCl2-Si02
Catalyst at Various Temperatures 168
3-9 Product Distribution from the Reaction of 1,2-
Dichloroethane with Ru(III)Cl3AlCl2-Si02
Catalyst at Various Temperatures 170
3-10 Product Distribution from the Reaction of 1,2-
Dichloroethane with K2 Pd(11)Cl4AlCl2-Si02
Catalyst at Various Temperatures 171
3-11 Product Distribution from the Reaction of 1,2-
Dichloroethane with Pd(II)Cl2AlCl2-Si02 {Type 1}
Catalyst at Various Temperatures 172
3-12 Comparison of all Catalysts Reacted with 1,2-
Dichloroethane at 100 C 173
3-13 Comparison of the PdCl2 and K2PdCl4 Doped Solid
Acid Catalysts {Type 1} 174
3-14 Comparison of the PdCl2 Doped Acid Catalysts
Prepared by Method I and Method II 175
3-15 Product Distribution for the Reaction of 1,2-
Dichloroethane with AlCl2-SiC>2 catalyst at
Various Reaction Temperatures 177
xiii


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Fhilosophy
TOE PREPARATION, CHARACTERIZATION AND
CATALYTIC ACTIVITY OF A NEW SOLID ACID CATALYST SYSTEM
By
Edward E. Getty
December 1988
Chairman: Russell S. Drago
Major Department: Chemistry
The preparation and use of solid strong acid catalysts and
superacids are active areas of research. Solid acids and superacids
are reported to exhibit extremely high catalytic activities for
reactions such as isomerization, cracking, hydrocracking,
dehydration, alkylation, acylation, conversion of methanol to
gasoline, and so forth. Recent research in this area has focused on
the preparation of stronger solid acids and their characterization.
Advantages of solid acid catalysts over liquid acid catalysts
include ease of separation from reaction mixture and high
selectivity or specific activity.
A series of novel solid strong acids has been prepared by
treatment of inorganic oxides by Lewis acids. The method of
creating or enhancing the number of tetrahedral aluminum centers on
inorganic oxides has led to a series of novel solid acid catalysts
which displays an increased acidity over the supports alone.
xiv


Investigations of acid sites by the infrared spectroscopy of
adsorbed pyridine, calorimetric titrations and solid-state nuclear
magnetic resonance on a series of new solid acid catalysts will be
discussed. This new solid acid catalyst system exhibits high
catalytic activity and selectivity for cracking reactions under
relatively mild conditions. In addition to the reactions of
hydrocarbons, the reactions of various polychlorinated molecules
have been studied.
xv


CHAPTER I
TNTRDDUCnO
Since the introduction of amorphous silica-alumina solid acids
over 40 years ago, catalytic cracking has become one of the world's
most important processes for the refining of petroleum. [1] The
popularity of the catalytic cracking process results from its
flexibility in treating a variety of feedstocks used in refinery
processes.[1-3] Temperatures of 450-550C and pressures of 1-2 atm
are typical reaction conditions.[2] Amorphous silica-aluminas and
zeolites are the most common catalysts used and recent trends in
catalytic cracking research are aimed at enhancing the acidity of
these catalysts.[4]
The preparation and use of strong solid acids and superacids as
catalysts are active areas of research.[4,5] These materials
exhibit extremely high catalytic activity for reactions such as
isomerization, cracking, hydrocracking, dehydration, alkylation,
acylation, conversion of methanol to gasoline, and so forth.[4,5]
Advantages of solid acid catalysts over liquid acid catalysts
include ease of separation from reaction mixture and high
selectivity or specific activity.[4]
In view of the higher activity of tetrahedral aluminum Lewis
acids than octahedral Lewis acids, we are interested in preparing
solids containing stable tetrahedral aluminum sites. As a result
1


2
of this research a new solid, strong acid catalyst system is
reported which exhibits high catalytic activity and selectivity for
catalytic cracking reactions under relatively mild conditions. In
the following chapters the synthesis, characterization, and
catalytic activity for these new solid acid catalyst systems are
reported.
The synthesis, characterization, and catalytic activity of
these catalysts for the catalytic cracking of hydrocarbons is
discussed in Chapter II. The synthesis and catalytic activity of
various solid acid catalysts doped with metals is discussed in
Chapter III. In addition to cracking, the dehydrochlorination and
hydrodechlorination of various polychlorinated hydrocarbons is
reported.


CHAPTER II
REACTION OF HYDROCARBONS
2.1 BACKGROUND
Since the introduction of acid-treated clays and amorphous
silica-alumina solid acids as cracking catalysts in the late 1930s,
catalytic cracking has become the most important process for the
refining of crude petroleum in the world. [1-3] In 1985 the
petroleum industry bought 370 million lbs of catalytic cracking
catalysts at a cost of 250 million dollars. The projected use of
catalytic cracking catalysts in 1990 is expected to increase to 405
million lbs which is worth 275 million dollars.[6] Because of the
large volumes of solid acid cracking catalysts used and the
importance of the petroleum refining process, a large amount of
research has been conducted in the area of solid acid and superacid
catalysis.[1-6]
Currently, the preparation and use of strong acid catalysts and
superacids are active areas of research. These materials exhibit
extremely high catalytic activity for reactions such as
isomerization, cracking, hydrocracking, dehydration, alkylation,
acylation, conversion of methanol to gasoline, and so forth.[5]
Because of the reported advantages of solid acid catalysts[4],
3


4
recent research has focused on the preparation and
characterization[2,4,5] of stronger solid acids.
Many attempts have been made to use metal halides as
homogeneous acid catalysts and one of the most frequently studied
inorganic Lewis acid metal halides is aluminum chloride. Aluminum
chloride was even tested commercially but was abandoned because of
technical difficulties such as corrosion, separation of phases,
difficulty in the recovery of the catalyst and the formation of high
molecular weight hydrocarbons.[2,3] As a result recent research has
focused on the anchoring of homogeneous acid catalysts onto
inorganic oxides for use as solid acid catalysts.[2-7]
Many patents have been issued for the treatment of inorganic
oxides with aluminum chloride. [8-15] The most common method of
treating hydroxylated inorganic oxides with aluminum chloride is by
vapor deposition.[4,8-14] The vapor deposition is conducted by
passing the vapors of aluminum chloride through the inorganic oxide
using a carrier gas such as helium[7,9,10,12,14] or sublimation of
the aluminum chloride from a mixture of the inorganic oxide and
aluminum chloride.[11,14] An alternative to the vapor deposition of
the aluminum chloride is the reaction of aluminum chloride and the
inorganic oxide in a chlorinated or hydrocarbon solvent. [8]
Past attempts[8] conducted on this reaction have employed
solvents other than carbon tetrachloride (CC14). It has been
determined that chloroform (CHC13), methylene chloride (CH2CI2),
ethylene dichloride (CICH2CH2CI) and saturated hydrocarbons (to name


5
a few) do not produce a solid acid catalyst with the properties
described for the reaction employing CC14.[15]
In each of these cases (except CCl4) aluminum chloride is
evolved fren the catalyst surface with time and only short term
activity results.[4,8-14] This is in contrast to what has been
found for the inorganic oxides treated with aluminum chloride in
CC14 by the procedure reported here. [15]
Since it is knewn that the catalytic properties of these
amorphous silica-alumina catalysts arises from the acidity[1-3] many
methods have been developed to characterize the acidity of these
catalysts.[1-3,16-25] Using changes in the infrared spectra of
adsorbed basic molecules on solid acids to determine the nature and
strength of the acid sites present has been practiced
extensively. [16-27] Seme of the early work in this area was
performed by E. Parry in the early 1960's. [16] In this method,
pyridine is allowed to interact with the solid acid surface and
changes in the infrared adsorptions in the 1400 cm-1 to 1700 cm-1
region for pyridine are measured. When pyridine is adsorbed on an
acid site which has protonic character, infrared adsorptions
indicative of pyridinium ion are observed at 1485-1500 cm-1, 1540
on-1, -1620 cm-1 and -1640 cm-1.[16-18] The infrared band at 1540
cm-1 involves the bending mode for pyridinium ion including the
C-N-C as well as the N+-H bending motion.[21-24] Since the 1540 cm
1 band is not present for pyridine bound to other Lewis acid sites,
it is used along with the other bands to characterize protonic
(Bronsted) sites.[16] When pyridine is adsorbed on a non-protonic


6
(Lewis) acid the infrared adsorptions indicative of coordinately
bound pyridine are observed at 1447-1460 on-1, 1488-1503 cm-1, -1580
cm-1 and 1600-1635 can-1.[21-24] The infrared band in the 1447-1460
cm-1 region involves the A^ bending mode, C-N-C, and is used to
characterize coordinatively bonded pyridine, Figure 2-1. As the
Lewis acid strength of the acid site increases the band is
reported[16] to shift to higher frequencies.
Extensive research has been conducted on the vibrational
spectra of benzene and pyridine. The assignments of the frequencies
have been reported in the literature.[27,28]
The use of solid-state Magic-Angle-Spinning (MAS) NMR
spectroscopy as a spectroscopic tool to characterize heterogeneous
catalysts has bee widely documented.[29-33] A large amount of work
has focused on the 27A1 and 29Si solid-state MAS NMR spectra of
silica-aluminas, aluminosilicates and zeolites.[29] By the use of
27A1 and 29Si MAS NMR spectroscopy it has been shewn that 4-
coordinate and 6-coordinate aluminum exhibit different chemical
shifts with large enough separation that they can be distinguished
even if they coexist in the same sample. [29,30]
It has been generally accepted that 4-coordinate aluminum, such
as that in zeolites, has a chemical shift in the 50-65 ppm region
relative to an Al3+(aq) standard. [30] A chemical shift of 58 ppm
relative to a Al3+(aq) standard has been observed for zeolitic
aluminum centers generated by the reaction of aluminum chloride with
ZSM-5 zeolite by vapor phase deposition.[33] The chemical shift for


7
/9b
Figure 2-1. The Bending Modes for Pyridine.


8
framework Al in gamma-Al203 has been reported to occur at 50 ppm
relative to an Al3+(aq) standard. [33] The 27A1 NMR of an aqueous
A1 (N03) 3 solution is the reference for all our 27A1 MAS NMR work.
Since the reference is a 6-coordinate octahedral complex, a peak
between 50 and 100 ppm down field from Al3+(aq) would be expected if
the aluminum chloride has retained its tetrahedral geometry. The
chemical shift for aluminum chlorahydrate is reported[31] to be 62.8
ppm versus Al3+(aq) which would be near the peak expected for a
surface-bound chloroaluminum species formed by the reaction of
aluminum chloride and a hydroxylated inorganic oxide, [8-14] Equation
2-1.
/
/
/
/
/
/
/
/
/
/
/
/
/
/
-O-H
\
O
/
-O-H
-O-H
-O-H
-O-H
-O-H
\
0
/
+ ai2ci6
>
/
/
/
/
/
/
/
/
/
/
/
/
/
/
-O-H
\
0\ Cl
/ \/
-O-Al
-O-H \
-O-H Cl
-o\
-0-A1-C1
\ /
0/
/
+ 3 HC1
(2-1)
The chemical shift for A12C16 in solution has been reported to occur
at 91-105 ppm and the chemical shift for A1C14- has been reported to
occur at 100-110 ppm depending on the solvent.[32]
When aluminum chloride reacts with an inorganic oxide (such as
silica gel), tetrahedral aluminum centers are formed on the oxide
surface.[8-14,34] These tetrahedral aluminum centers should have
properties similar to free aluminum chloride and hence should have


9
similar catalytic activity. It can be determined using solid-state
MAS NMR if the aluminum chloride that is reacted with an inorganic
oxide has retained its tetrahedral conformation. Furthermore, the
27A1 chemical shifts for Al2Clg and A1C14 are much higher than for
the oxychloroaluminum species. It should be easy to distinguish the
A12C16 and A1C14 species from surface bound oxyaluminum species by
27A1 MAS NMR.
The following chapter is concerned with the preparation of
aluminum chloride treated inorganic oxides by a previously
unreported method. [15] The characterization by Infrared and NMR
spectroscopy as well as an in depth study of the catalytic activity
of the aluminum chloride treated supports is discussed to support
the claim that a new solid, strong acid has been discovered with
this new method of preparation.
2.2 EXPERIMENTAL
Reagents
All metal halides were used as purchased unless otherwise
stated. The palladium (II) chloride (P1C12) and rhodium (II)
chloride (RhCl3) were purchased from Aldrich Chemical Company
(Aldrich). Aluminum chloride (A12C16) with a purity of 99.997% was
purchased from Alfa Products. The iron (III) chloride (FeCl3) and
antimony (V) chloride (SbCl5) were purchased frcan AESAR. All
solvents were purchased from Fisher Scientific Co. (Fisher) except
tetrachloroethylene which was purchased from Eastman Kodak Co.


10
(Kodak), n-dodecane and n-hexadecane which were purchased from Alfa
Products. Carbon tetrachloride, chloroform and methylene chloride
were dried over phosphorous (V) oxide (Fisher). Benzene was dried
by distillation over calcium hydride. Cyclohexane and chloroform
(containing ethanol as a stabilizer) were purified by passage
through an activated alumina column. Tetrachloroethane, n-pentane,
n-hexane, n-heptane, n-dodecane, n-hexadecane and cumene were used
as purchased. Gold label (99+%) pyridine was purchased from Aldrich
and was used without further purification. All solvents were stored
over 4A molecular sieves (Davison Chemical). The gaseous reactants
methane, dimethyl ether, propylene, prepane, isobutane, technical
grade hydrogen chloride (99.0%), and C.P. Grade carbon monoxide
(99.5%) were purchased frcm Matheson. Hydrogen, helium, argon and
nitrogen were supplies by Aireo and Liquid Air. The semiconductor-
grade hydrogen chloride (99.995%) was purchased from Air Products.
The supports used for the preparation of the catalysts are silicon
dioxide (SO2)/ alumina (AI2O3), high-silica zeolite (silicalite),
Y-zeolite (LZ-Y82), boron oxide (B2O3), titanium dioxide (Ti02) and
magnesium oxide (MgO). All support materials were used as purchased
unless otherwise stated. For the silicon dioxide supports the
primary material was Davison Grade #62 silicon dioxide (donated by
W.R. Grace Co.) with a surface area of 340 rr^/gram, pore volume of
1.1 cn^/gram and a mess size of 60-200. [35] The three types of
silicon dioxide support materials used for surface area dependence
studies were purchased frcm AESAR. All three supports are 60-325
mesh size with surface areas of 215 xi^/gram, 420 m2/gram, 690


11
ir^/gram and pore volumes of 1.0 cm3/gram, 0.8 cm3/gram and 0.4
cin3/gram, rejectively. The alumina support, acid Brockman Activity
I (80-120 mesh), had a surface area of 180 n^/gram. [35] A high-
silica zeolite which was donated by Union Carbide had a surface area
of 400 n^/gram and a pore volume of 0.19 cm3/gram. Hie Y-zeolite
was a Linde LZ-Y82 molecular sieve purchased from Alfa Products and
is used commercially as a fluid catalytic cracking (FCC) catalyst.
The boron oxide was purchased from AESAR and had a mesh size of 60.
Bayer AG donated the hydroxylated titanium dioxide (surface area 200
it^/gram) and the magnesium oxide was purchased from Fisher. 5,5-
dimethyl- 1-pyrrol ine-1-oxide (EMPO) which is a diamagnetic spin
trapping agent was purchased from Aldrich. Other reactants used for
cracking reactions were activated carbon (Curtin, MCB) and res id
(FHC-353 donated by Amoco) which is a mixture of high molecular
weight hydrocarbons obtained from the distillation of heavy crude
oil. Monomers used for polymerization reactions were isobutane
(Matheson), styrene (Fisher), methyl methacrylate (Fisher),
methacrylate (Fisher), vinyl acetate (Aldrich), ethyl vinyl ether
(Aldrich) and epichlorohydrin (Kodak). Purification of monomers
were conducted by literature methods.
Instrumentation
All air and water sensitive manipulations were performed in a
Vacuum Atmosphere Company model HE-43-2 inert atmosphere box or in
an Aldrich inert atmosphere glove bag. All syntheses were conducted
under a nitrogen or argon atmosphere and one atmosphere pressure.


12
Routine GC analysis for hydrocarbon products were performed on a
model 940 FID Varian gas chromatograph equipped with a Hewlett-
Packard 3390A integrator and a 1/8 inch by 8 foot stainless steel
Porapak Q (100-120 mesh) column or a 1/8 inch by 6 foot stainless
steel Hayesep Q (80-100 mesh) column. Routine GC analysis for
chlorinated hydrocarbons were performed on a model 3700 TCD Varian
gas chromatograph equipped with a Hewlett-Packard 3390A integrator
and a 1/8 inch by 8 foot Porapak Q (100-120 mesh) column. The GC
FTTR was performed on a Nicolet 5DXB FTXR spectrometer equipped with
a Nicolet GC interface and a Hewlett-Packard 5890A gas chromatograph
using a 1.5 micron thick DB 130m fused silica capillary column that
was 30 meters in length. EFR spectra were obtained from a Bruker
ER200D-SRC spectrometer equipped with a variable temperature unit,
ER 022 signal channel controller, ER 001 time base controller, ER
031M field controller, ER 082 power supply and ER 040XR microwave
bridge. GC mass spectrometry was performed by Dr. Roy King of the
Microanalytical laboratory, University of Florida, Gainesville,
Florida. Gas samples were analyzed on a AEI MS 30 mass spectrometer
with a KDIT0S DS55 data station. The system was connected to a PYE
Unicam 104 gas chronatograph equipped with a 1/4 inch by 5 foot
glass Porapak Q (100-120 mesh) column. Solid-state magic angle
spinning (MAS) nuclear magnetic resonance spectra were collected by
Dr. W. S. Brey of the University of Florida, Gainesville, Florida,
on a Nicolet NT-300 300 mHz wide-bore superconducting FT-NMR
spectrometer. Infrared spectra were obtained as mulls on a nicolet
5DXB FT-IR spectrometer using KBr plates. All solid-liquid phase


13
cracking reactions and polymerizations were carried out in 250 mL or
500 mL Parr pressure bottles equipped with a brass or stainless
steel swagelok pressure heads and neoprene stoppers.[36]
Fixed Bed Flew Reactor
A fixed-bed flew reactor was constructed as described by Keith
Weiss and reported in his Ph.D. Dissertation. [35] The reactor was
modified by placing a hydrocarbon bubbler after the reactant gas
bubblers and before the catalyst zone to allcw the addition of a
hydrocarbon substrate. The modified reactor allowed the
experimenter to saturate the reactant and carrier gases with any
liquid hydrocarbon substrate that has an appreciable vapor pressure.
Ihe flew rates of the individual gases were controlled by teflon
needle valves. Hydrogen and helium were passed through mineral oil
bubblers whereas the HC1 was bubbled through sulfuric acid. The
gases were allowed to mix and pass through bubbler which contained a
hydrocarbon/carbon tetrachloride mixture. This gas mixture was then
allowed to flew through a catalyst which was supported on a glass
frit. The catalyst zone was heated by a Thermolyne Briskheat
flexible electric heat tape controlled by an Omega Engineering, Inc.
digital temperature controller, model CN 310 equipped with a J-Type
thermocouple. Pregas and post gas samples for GC analysis could be
obtained through sample ports before and after the catalyst zone.
Overall flew rates for the reactor system were monitored by a
calibrated bubble flew meter. The entire reactor was constructed of
glass and was custom built by glass blowers Rudy Schroschein and


14
Dick Moshier at the glass shop, University of Florida, Gainesville,
Florida.
This reactor was further modified using a syringe pump to
deliver liquid reactants to the catalyst in place of a hydrocarbon
or hydrocarbon/carbon tetrachloride bubbler.[37] A preheater zone
was added to the system to ensure proper mixing and heating of all
reactants before they were contacted with the catalyst. Typically
only one gas was used as a carrier gas and/or reactant gas. The gas
flew rate was regulated by a calibrated rotoflcw meter purchased
from Gilmont Instruments, Inc.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using Carbon Tetrachloride as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 10.20
grams of silica gel (washed with 1M HC1 and dried under vacuum at
80C for 72 hrs) and 150 mL of carbon tetrachloride (dried over 4 A
sieves). After purging the system with nitrogen (N2), 5.10 grams of
anhydrous aluminum chloride (A12C16) was added and the mixture was
allowed to stir at reflux under a N2 atmosphere for 1-5 days in the
absence of light.
After approximately 1 hour the mixture developed a purple
color. This color continued to increase in intensity until the
mixture was black in appearance (~8 hours).
After 5 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was burgundy in color and was utilized as the


15
catalyst material for the cracking experiments described later in
this chapter. The catalyst was water-sensitive and turned white on
exposure to moisture.
The catalyst gave an EH* signal indicative of a free-radical
with a g value of 2.012, Figure 2-2. If after the purple color
first appears, to approximately 1 days, the mixture is filtered, the
catalyst obtained will show an EPR signal which is very broad and
has a g value of 2.06, Figure 2-3.
Preparation of an Alumina Catalyst Doped with Aluminum Chloride
Using Carton Tetrachloride as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 15.0
grams of alumina (dried at 150C) and 175 mL of carbon tetrachloride
(dried over 4 A sieves). After purging the system with nitrogen
(N2), 7.5 grams of anhydrous aluminum chloride (A12C16) was added
and the mixture was allowed to stir at reflux under a N2 atmosphere
for 2 days in the absence of light.
After approximately 1 hour the mixture developed a purple
color. This color continued to increase in intensity until the
mixture was black in appearance.
After 2 days the reaction mixture was filtered under an N2
atmosphere. The filtrate had a slight red color and the resulting
solid product obtained was purple in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.


16
Figure 2-2. An EFR Spectrum of a Heterogeneous Acid Catalyst
Before Complete Reaction.


17
- 2.0!
Figure 2-3. An EFR Spectrum of a Heterogeneous Acid Catalyst
After Ccrplete Reaction.


18
Preparation of a High-Silica Zeolite Catalyst Doped with Aluminum
Chloride Using Carton Tetrachloride as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 10.0
grams of zeolite (dried at 250 C under vacuum) and 150 mL of carbon
tetrachloride (dried over 4 A sieves). After purging the system
with nitrogen (N2), 5.0 grams of anhydrous aluminum chloride
(A^Clg) was added and the mixture was allowed to stir at reflux
under a N2 atmosphere for 5 days in the absence of light.
After approximately 1 hour the mixture developed a bright
yellow color. After 2 days the reaction mixture was filtered under
an N2 atmosphere. The filtrate had a slight yellow color and the
resulting solid product obtained was bright yellow in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Y-Zeolite Catalyst Doped with Aluminum Chloride
Using Carbon Tetrachloride as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 23.9
grams of zeolite (dried at 300C under vacuum) and 250 mL of carbon
tetrachloride (dried over 4 A sieves). After purging the system
with nitrogen (N2), 13.29 grams of anhydrous aluminum chloride
(A12C16) was added and the mixture was allowed to stir at reflux
under a N2 atmosphere for 2 days in the absence of light.


19
After approximately 1 hour the mixture developed a tan color.
After 2 days the reaction mixture was filtered under an N2
atmosphere. The filtrate had a pale brown color and the resulting
solid product obtained was tan in appearance. The catalyst was
water-sensitive and turned white on exposure to moisture.
Preparation of a Boron Oxide Catalyst Doped with Aluminum Chloride
Using Cartoon Tetrachloride as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 15.0
grains of boron oxide (dried at 80 C under vacuum) and 250 mL of
carbon tetrachloride (dried over 4 A sieves). After purging the
system with nitrogen (N2), 7.50 grams of anhydrous aluminum chloride
(A12C16) was added and the mixture was allowed to stir at reflux
under a N2 atmosphere for 3 days in the absence of light.
After approximately 1 hour the mixture developed a purple
color. This color continued to increase in intensity until the
mixture was black in appearance.
After 3 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was black in color.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EER signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.


20
Preparation of a Titanium Dioxide Catalyst Doped with Aluminum
Chloride Usim Carton Tetrachloride as a Solvent
In a 500 mL 1-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 30.0
grams of titanium dioxide and 300 mL of carbon tetrachloride (dried
over 4 A sieves). After purging the system with nitrogen (N2), 15.0
grams of anhydrous aluminum chloride (A12C16) was added and the
mixture was allowed to stir at reflux under a N2 atmosphere for 3
days.
After approximately 1 hour the mixture developed a slight pink
color which gradually increase in intensity until the mixture was
peach in color.
After 3 days the reaction mixture was filtered under an N2
atmosphere. Ihe filtrate was colorless and the resulting solid
product obtained was peach in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EPR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.013.
Preparation of a Magnesium Oxide Catalyst Doped with Aluminum
Chloride Usina Carbon Tetrachloride as a Solvent
In a 250 mL 1-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 15.0
grams of magnesium oxide and 150 mL of carbon tetrachloride (dried
over 4 A sieves). After purging the system with nitrogen (N2), 7.5
grams of anhydrous aluminum chloride (A12C16) was added and the


21
mixture was allowed to stir at reflux under a N2 atmosphere for 3
days.
After approximately 1 hour the mixture developed a slight pink
color which gradually increase in intensity until the mixture was
bright pink in color.
After 3 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was pink in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using Chloroform as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 10.20
grams of silica gel (washed with 1M HC1 and dried under vacuum at
80C for 72 hrs) and 150 mL of chloroform (dried over 4 A sieves).
After purging the system with nitrogen (N2), 5.10 grams of anhydrous
aluminum chloride (A12C16) was added and the mixture was allowed to
stir at reflux under a N2 atmosphere for 5 days.
After approximately 1 hour the mixture developed a purple
color. This color continued to increase in intensity until the
mixture was black in appearance.
After 5 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was burgundy in color.


22
Hie catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using Methylene Chloride as a Solvent
In a 500 mL 1-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 10.16
grams of silica gel and 200 mL of methylene chloride (dried over 4
A sieves). After purging the system with nitrogen (N2), 5.07 grams
of anhydrous aluminum chloride (A12C16) was added and the mixture
was allowed to stir at reflux under a N2 atmosphere for 5 days.
After 5 days the light purple reaction mixture was filtered
under an N2 atmosphere. The filtrate was colorless and the
resulting solid product obtained was light purple in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EPR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using 1.2-Dichloroethane as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 5.00
grams of silica gel (washed with 1M HC1 and dried under vacuum at
80C for 72 hrs) and 175 mL of 1,2-dichloroethane (dried over 4 A
sieves). After purging the system with nitrogen (N2), 2.50 grams of


23
anhydrous aluminum chloride (A12C16) was added and the mixture was
allowed to stir at reflux under a N2 atmosphere for 5 days.
After approximately 1 hour the mixture developed a purple
color. This color continued to increase in intensity until the
mixture was black in appearance.
After 5 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was burgundy in color.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using n-Hexane as a Solvent
In a 500 mL 1-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 10.16
grams of silica gel and 200 mL of n-hexane (dried over 4 A sieves).
After purging the system with nitrogen (N2), 5.07 grams of anhydrous
aluminum chloride (A12C16) was added and the mixture was allowed to
stir at reflux under a N2 atmosphere for 3 days.
After 3 days the bright yellow reaction mixture was filtered
under an N2 atmosphere. The filtrate was colorless and the
resulting solid product obtained was yellcw in appearance.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.011.


24
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using Cyclohexane as a Solvent
In a 250 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 5.00
grams of silica gel (washed with 1M HC1 and dried under vacuum at
80 C for 72 hrs) and 175 mL of cyclohexane (dried over 4 A sieves).
After purging the system with nitrogen (N2), 2.50 grams of anhydrous
aluminum chloride (A12C16) was added and the mixture was allowed to
stir at reflux under a N2 atmosphere for 16 hours.
After 16 hours the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was light yellew in color.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signed, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride
Using Benzene as a Solvent
In a 1000 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 100 grams
of silica gel (washed with 1M HC1 and dried under vacuum at 80 C for
72 hrs) and 750 mL of benzene (dried over 4 A sieves). After
purging the system with nitrogen (N2), 50 grams of anhydrous
aluminum chloride (A12C16) was added and the mixture was allowed to
stir at reflux under a N2 atmosphere for 2 days.
After 2 days the reaction mixture was filtered under an N2


25
atmosphere. The filtrate was colorless and the resulting solid
product obtained was black in color.
The catalyst was water-sensitive and turned white on exposure
to moisture. The catalyst gave a sharp EFR signal, similar to
Figure 2-3, indicative of a free-radical with a g value of 2.012.
Preparation of a Silica Gel Catalyst Doped with Aluminum Chloride by
Vapor Deposition
In a sublimation apparatus 3 grams of aluminum chloride and 5
grams of silicon dioxide (washed with lM HC1 and dried under vacuum
at 80 C for 72 hrs) were physically mixed and heated under vacuum at
240C to sublimed the aluminum chloride through the support. After
all of the aluminum chloride was removed from the sample the support
was heated to 350C to remove any excess aluminum chloride.
The same procedure was also repeated using alumina as the
support material.
Preparation of a Palladium (ID Chloride-Aluminum Chloride Doped
Catalyst Using Carbon Tetrachloride as a Solvent
In a 200 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 5.0 grams
of silica gel (washed with 1M HC1 and dried under vacuum at 80 C for
72 hrs), 0.06 grams palladium (II) chloride (PdCl2) and 100 mL of
carbon tetrachloride (dried over 4 A sieves). The reaction mixture
was stirred and heated at reflux under a nitrogen (N2) atmosphere
for 6 hours. Next 2.61 grams of anhydrous aluminum chloride


26
(A12C16) was added and the mixture was allowed to stir at reflux
under a N2 atmosphere for 2 days.
After 2 days the reaction mixture was filtered under an N2
atmosphere. The filtrate was colorless and the resulting solid
product obtained was orange in color.
The catalyst was water-sensitive and turned light peach on
exposure to moisture.
Preparation of a Rhodium (IIP Chloride-Aluminum Chloride Doped
Silica Gel Catalyst Using Carton Tetrachloride as a Solvent
In a 200 mL 3-neck round bottom flask equipped with a reflux
condenser and a teflon coated magnetic stir bar was placed 9.0 grams
of a 2% rhodium (III) chloride (RI1CI3) on silica gel (prepared as
above for palladium), 5.0 grams aluminum chloride, and 150 mL of
carbon tetrachloride (dried over 4 A sieves) .Ihe reaction mixture
was allowed to stir at reflux under a N2 atmosphere for 24 hours.
After 24 hours the reaction mixture was filtered under an N2
atmosphere. Ihe filtrate was colorless and the resulting solid
product obtained was orange in color.
The catalyst was water-sensitive and turned light orange on
exposure to moisture.
Procedure for the Adsorption of Pyridine onto Supports and Solid
Acid Catalysts for the Characterization of Acid Sites
The infrared spectra of pyridine on solid acid catalysts has
long been used for characterization of the acid sites on solid acid
catalysts. [16,17,20-25] The procedure used to adsorb and desorb


27
pyridine was similar to that reported previously[16,17] with the
exception that our samples were in pender form and not in pressed
wafers. This meant that quantitative infrared measurements of the
acid site concentrations could not be performed and only a
qualitative determination of the nature of the acid sites could be
made. Support and catalysts samples were dried at 200C for 8 hours
under vacuum prior to the adsorption experiments. Pyridine vapors
were be contacted with the catalyst at room temperature for 2 to 3
hours and then the catalyst was placed under vacuum to remove any
excess pyridine (2-3 hours). A sample of the support or catalyst
was removed and a fluorolube mull prepared. An IR spectrum was
obtained in the region from 1700 cm-1 to 1400 cm-1 in order to
characterize the type of acid sites present. The sample was then
evacuated at 150C, 225C and 300C for 2 to 3 hours at each
temperature. An IR spectrum was obtained after evacuation at each
temperature. The results of these experiments are discussed in a
later section.
Procedure for the Spin Trapping of Radicals on Solid Acid Catalysts
Using CMFO
All manipulations were conducted in an inert atmosphere box.
Powder samples of the catalysts were added to quartz EPR tubes that
contained carbon tetrachloride or toluene. An amount of EMPO was
added to this mixture that corresponded to the number of moles of
aluminum chloride contained in the sample. The EFR spectra were
collected in the usual manner. Computer simulations of the spin
trapped radicals were performed using the program QP0W[38,39] as


28
modified by J. Telser[40] and N.M. Wong of the University of
Florida, Gainesville, Florida.
2.3 RESUIITS AND DISCUSSION
Preparation of a New Solid Acid Catalyst
As described in the experimental section the catalysts are
prepared by the reaction of the hydroxyl groups of an inorganic
oxide with aluminum chloride (A12C16) in refluxing carbon
tetrachloride (0C14), Equation 2-2. The reaction of aluminum
chloride with silicon
/
/
/
/
/
/
/
/
/
/
/
/
/
/
-OH
\
0
/
-OH
-OH
-OH
-OH
-OH
\
0
/
+ ai2ci6
/
/
/
/
/
/
Reflux /
>/
cci4, n2 /
/
/
/
/
/
-OH
\
0\ Cl
/ \/
-OA1
-OH \
-OH Cl + 3 HC1
-o\
-OA1-C1
\ /
0/
/
(2-2)
dioxide was monitored by accurately weighing the aluminum chloride
and silicon dioxide before the reaction. When the weight of the
resulting aluminum chloride doped silica gel was subtracted from the
sum of the weights of the starting materials used in the reaction it
was determined that 1.1 moles of hydrogen chloride (HC1) was evolved
for every mole of A1C13 used. This suggests that over 90% of the
chloroaluminum species on the catalyst surface of this support has


29
the ccrtposition (-0-)AlCl2. Since the average composition is two
chlorides per aluminum and A12C16 would sublime off upon heating
(which does not occur) there is very little (-0-)2A1C1 present. A
blank reaction between Si02 and 0C14 shewed no HC1 evolution and the
resulting solid did not have any acidic properties as indicated by
pyridine adsorptions. This result is consistent with literature
reports in that CC14 does not chlorinate the surface of silica gel
belcw a temperature of 350C.[41]
Past attempts[8] conducted on this reaction have employed
solvents other than CC14. It has been determined that chloroform,
methylene chloride, ethylene dichloride and saturated hydrocarbons
(to name a few) do not product a solid acid catalyst with the
properties described for a solid acid prepared in CC14.[15] Several
patents have been issued for the treatment of inorganic oxides with
aluminum chloride to form strong acid catalysts.[5,8-14] In each of
these cases aluminum chloride is rapidly evolved from the surface
and only short term activity results. [4,5,8-14] This is in contrast
with what has been found for the aluminum chloride doped inorganic
oxides prepared in CC14.
The new catalysts reported in the experimental section have
been characterized by IR spectroscopy, solid-state MAS NMR
spectroscopy and calorimetric titration. As detailed in latter
sections these aluminum chloride doped inorganic oxides are
catalysts for a wide range of acid catalyzed reactions.


ABSORBANCE
30
WAVENUMBERS (CM-1)
Figure 2-4. Infrared Spectrum of SO2 Dried at 200"C.


AB50RBANCE
31
vYAVENUUBERS I CM1 )
Figure 2-5. Infrared Spectrum of SiC>2 After Pyridine
Adsorption and Evacuation at Roan Temperature.


ABSORBANCE
32
WAVENUMBERS (CM-I)
Figure 2-6. Infrared Spectrum of SO2 After Pyridine
Adsorption and Evacuation at 150C.


33
Characterization of the New Solid Acid Catalysts by the Infrared
Spectroscopy of Adsorbed Pyridine
Using the procedure outlined in the experimental section a
sample of the silicon dioxide was dried under vacuum at 200 C for 8
hours and three IR spectra were collected. The three IR spectra are
shewn in Figures 2-4 to 2-6. The IR spectrum shewn in Figure 2-4 is
of the silicon dioxide after drying at 200C under vacuum. This
relatively featureless spectrum is typical of the inorganic oxides
used. After pyridine is adsorbed onto the silica gel surface and
all excess pyridine is removed by evacuation at room temperature,
two bands that are indicative of hydrogen bonded pyridine appear,
Figure 2-5. The band at 1447 cm-1 is attributed to the interaction
of pyridine with the hydroxyl groups of the silica gel and results
from hydrogen bonding since it is known that unmodified silicon
dioxide has no strong acidic or basic properties. [16,19] This band
is located at 1438 cm-1 for free pyridine. When the silicon dioxide
is evacuated at 150C all of the adsorbed pyridine is removed
indicating that the pyridine interacts only weakly with the surface
of the support, (see Figure 2-6). The results obtained on the
silicon dioxide material parallel the results obtained by Parry [16]
for silicon dioxide and indicates that the experimental method being
used is valid.
Next a sample of the silicon dioxide doped with A12C16
(AICI3/SO2) which had been prepared in CC14 was dried at 200"C for
8 hours. The infrared spectrum of the dried AICI3/SO2 is similar
to the IR spectrum of the dried silicon dioxide, Figure 2-7. When
pyridine is adsorbed onto the AICI3/SO2 catalyst and evacuated at


ABSORBANCE
34
WAVENUMBERS (CM1)
Figure 2-7. Infrared Spectrum of AlCl2-SiC>2 Dried at 200 C.


35
roan temperature, bands indicative of both Bronsted and lewis acid
sites are observed, Figure 2-8. The large band at 1540 cm-1 results
from pyridinium ion which is formed by the protonation of pyridine
by Bronsted acid sites. lewis acid sites cure indicated by the
presence of a band at 1449 cm-1. Since the IR spectrum is obtained
after evacuation at room temperature, there is seme hydrogen bonded
pyridine present on the surface and is responsible for the broad
shape of the Lewis acid band. The peak at ~1499cm-1 is a band
present in both Bronsted and Lewis acid bound pyridine and cannot be
used to distinguish between the two types of acid sites[16]. After
evacuation at 150C, to remove any hydrogen bound pyridine, the peak
for the Lewis acid bound pyridine is centered at 1456 an-1, Figure
2-9. This is a shift of 18 cm-1 and is comparable to shifts
reported in the literature for solid acid cracking catalysts.[16]
In addition to a shift in the Lewis acid band for pyridine there is
a large amount of Bronsted acid sites present as indicated by the
band at 1540 cm-1. Even after evacuation at 300C both Bronsted and
Lewis acid sites are present indicating a very strong interaction
between the surface of the solid acid and the adsorbed pyridine,
Figure 2-10. The results for this catalyst are in good agreement
with the data obtained by Parry[16] and other workers in the
area[17] for commercial amorphous silica-aluminas and zeolites. A
summary of the infrared shift data for pyridine adsorbed onto
various aluminum chloride treated inorganic oxides (A1C12-X; X=
inorganic support) is presented in Table 2-1.


ABSORBANCE
36
WAVENUMBERS (CU-l)
1 1554-
I 2757
0.7889
0347
7233
7342
) 269
031 7
8444
Figure 2-8. Infrared Spectrum of AlCl2-Si02 After Pyridine
Adsorption and Evacuation at Room Temperature.


ABSORBANCE
37
B
1700 0 1650.0 1600 0 1550 0
WAVENUUBERS
Li&lB
\ J Peak List
X-.
1456
5
Y-
0.7534
X-
1473
4
Y-
0.6716
X-
1 487
9
Y-
0. 3626
X-
1506
4
Y-
0 5933
X-
1539
6
Y=
0 7337
X-
1559
1
Y-
0. 5572
X-
1570
5
Y-
0. 5213
X-
1576
2
Y-
0.5357
X-
1616
4
Y-
0 7640
X-
1636
7
Y-
0 7713
X-
1653
4
Y-
0 6719
1 500.0 1 450.0 i400.0
(CU1)
. Infrared Spectrum of AlCl2-Si02 After Pyridine
Adsorption and Evacuation at 150C.
Figure 2-9


ABSORBANCE
38
WAVENUMBERS (CM-1)
6387
58*8
6799
5*08
52*0
5226
5826
6*0)
6 1 88
66 l 2
6 108
Figure 2-10
Infrared Spectrum of AlCl2-SiC>2 After Pyridine
Adsorption and Evacuation at 300C.


39
Table 2-1. Infrared Shift Data for Pyridine Adsorbed onto
AlCl2-X Catalysts.
X SOLVENT SHIFT OF LEWIS BANE^
sio2
0C14
18.0
ai2o3
CC14
15.2
Silicalite***
CC14
18.1
B2O3
CC14
18.1
TiOz
0C14
14.1
MgO
CC14
7.8
SO2
CHCI3
9.3
S02
ch2ci2
8.6
SO2
C6Hl4
8.9
Si2
C6H6
8.3
* This solvent was used to prepare the catalyst.
** This shift is measured after purrping at 150 C on the sample
exposed to pyridine. The free pyridine band occurs at
1438.5 cm-1.
*** A hic£i silica zeolite.


40
As seen in Table 2-1 the acid treated SO2, silicalite and B2O3
supports resulted in the largest shifts for the Lewis acid band.
Alumina and titanium dioxide exhibited shifts in an intermediate
range with magnesium oxide resulting in the lowest shift. The
frequency shifts listed are after evacuation at 150C to remove any
weakly hydrogen bound pyridine. The lew shift for MgO is not
unexpected due to the fact that magnesium oxide is basic [19] and the
resulting material formed from reacting a strong acid with a base
would result in a product that is weakly acidic in nature. Even
though the shift in the Lewis acid band for the MgO catalyst issmall
and in the range that would normally represent hydrogen bonded
pyridine, the band is still present after evacuation at 150C and
considered to arise form a Lewis acid-base interaction.
Several catalysts were prepared by methods described in the
patent literature and the results of the pyridine adsorptions are
listed at the bottom of Table 2-1. All patented catalysts that were
used employed silicon dioxide as the support material and solvents
other than CC14. For each of the solvents used a shift of only 8 or
9 cm-1 was observed after evacuation at 150C. An explanation for
the decrease in frequency shifts upon changing from carbon
tetrachloride to other solvents may be that each of the other
solvents contain reactive hydrogens or are basic molecules. It is
well known that aluminum chloride can react with organic compounds
to form ionic complexes as shown in Equations 2-3 and 2-4.[42] When
solvents such as chloroform, methylene chloride and saturated


2 R-H + A12C16
41
2 R+HA1C13"
>
(2-3)
2 R-Cl + A12C16
> 2 R+A1C14"
(2-4)
hydrocarbons are employed, the aluminum chloride can react with the
solvent to form halo organo-aluminum complexes. [42] For solvents
with available hydrogens the reaction that may then take place is
abstraction of a hydride ion from the organic halide generating an
aluminum hydride and a carbonium ion. [43] The carbonium ion may
abstract a hydride ion from another solvent molecule or the support
material forming a neutral species. The aluminum hydride complex
may react with the support material, liberating HC1 and forming a
chloroaluminum hydride complex. This species is less acidic than
the chloroaluminum species formed when pure A12C16 is reacted with
the support material, Equations 2-5 and 2-6. Many other reactions
are possible between the aluminum chloride and the reaction medium.
The point to be made is that in solvents that contain carbon-
hydrogen
/
/
H
/
/
/
/
-O-H
/
-O-Al
/
\
/
\ / \
/
0
/
0/ Cl
/
/
/
/
/
-O-H
> /
-O-H Cl
/
-O-H
/
-O-H /
/
-O-H
/
-O-Al
/
\
/
\ / \
/
0
/
0/ H
/
/
/
/
/
/
H2A12C14
+
+ 2 HCl
(2-5)


42
/
/
/ -OH
/ \
/ o
/ /
/ C1
/ /
/ -OA1
/ \ / \
/ 0/ C1
/ /
A12C16 + / -OH
> / -OH C1 + 2 HC1
(2-6)
/ -OH
/ -OH
/ \
/ o
/ /
/
/ -0-H/
/ -OA1
/ \ / \
/ 0/ C1
/ /
/
bonds reactions involving aluminum-chlorine bonds that result in
the decomposition of the aluminum chloride into aluminum hydride or
organo-aluminum species that would exhibit lcwer acidity than
aluminum chloride alone may occur[43,44]. A reason for the decrease
in acidity for the catalyst prepared in benzene is that benzene is a
good tt-base and would form an acid-base complex with the aluminum
chloride. The ccmplexed aluminum chloride would be a weaker acid
than the free aluminum chloride. On the other hand, a fully
chlorinated solvent such as carbon tetrachloride will undergo an
exchange of chloride ion with aluminum chloride and will result in
no net reaction, Equations 2-7 to 2-9.
2 C13CC1 + A12C16 > 2 Cl3CfAlCl4 (2-7)
2 Cl3CfAlCl4_ > 2 C13CC1 + A12C16 (2-8)
2 C13CC1 + A12C16 > 2 C13CC1 + Al2Cl6 (2-9)


43
The result of this reaction is that the aluminum chloride is
stabilized in solution by the carbon tetrachloride. Since the
aluminum chloride cannot react with the solvent the aluminum
chloride is forced to react with the hydroxyl groups of the support
material.
The trend for the frequency shifts of the Lewis acid band for
pyridine can be clearly seen in Table 2-1. A neutral support such
as silica gel exhibits the highest shift along with a high silica
zeolite and boron oxide (B2O3). Acidic supports such as alumina and
titanium dioxide have the next largest shifts and the basic support
magnesium oxide exhibits the lowest frequency shift. An explanation
involving the acidic or basic properties of each support would be
acceptable except that boron oxide is not a neutral support. Boron
oxide has a structure which contains trigonal B03 units and has the
same acidic properties.[45] Because of the acidity associated with
boron oxide it would be expected that boron oxide would exhibit a
frequency shift for Lewis acid bound pyridine similar to that
exhibited by alumina. It should be stated that the same Lewis acid
is used to treat each support and would not be the controlling
factor in determining the frequency shift of the Lewis acid bound
pyridine if the support was not interacting with the acid center.
The shift in the Lewis acid band is a result of an inductive
effect involving the donation of the nitrogen lone pair of the
pyridine to a vacant orbital on a Lewis acid such as aluminum
trichloride (AICI3). As electron density is drawn away from the
nitrogen the pTF-pTT interaction between the ring carbons increases


44
resulting in an increase in the ring bending frequency for pyridine.
It has been previously reported that as the strength of the Lewis
acid increases the Lewis acid band for pyridine will shift to higher
frequencies.[16] This is a direct result of the increased electron
withdrawing strength of the Lewis acid. In the case of the
inorganic oxides treated with aluminum chloride, the strength of the
chloroaluminum center resulting from aluminum chloride should be the
same for each oxide. A difference in the electron withdrawing
strength of the acids would arise from the electronegativity of the
oxides themselves.
The Pauling electronegativity values for each of the elements
in the inorganic oxides are as follows: boron= 2.0, silicon^ 1.8,
aluminum= 1.5, titanium= 1.5 and magnesium= 1.2. [46] This trend in
electronegativities (Pauling and Mulliken) correlates with the trend
in the frequency shifts of the Lewis acid bound pyridine and may
contribute to the observed trend in the acid strengths. The trend
in the activities of these materials for the catalytic cracking of
hydrocarbons will be discussed in greater detail in a later section.
Characterization of a New Solid Acid Catalyst by A1 and ^Si
Solid-State Magic Angle Spinning (MAS) FT NMR Spectroscopy
The following discussion is concerned with the solid-state MAS
NMR spectra of the inorganic oxide treated with aluminum chloride as
described in the experimental section of tjiis chapter.
The first material examined was a catalyst which had been
prepared by refluxing Si02 and A12C16 in CC14 with enough water
present to hydrolyze all the A12C16 in order to determine the


45
spectrum of a decotposed catalyst. If a catalyst were prepared in
the presence of water or a good catalyst is exposed to water, it
would be expected that the aluminum chloride would be hydrolyzed and
form a 6-coordinate aluminum species. The catalyst prepared in the
presence of water (Figure 2-11) shews only one aluminum peak
centered at 0 ppm for the 27A1 MAS NMR which is indicative of 6-
coordinate aluminum. Figure 2-12 (which is referenced to IMS) shows
the 29si MAS NMR for the catalyst prepared in the presence of water
and indicates that there is only one type of silicon present which
is the 4-coordinate silicon of silicon dioxide. The broad peak
centered at -110 ppm relative to IMS is consistent with reports in
the literature for the 29Si MAS NMR of silica gels and silicalite
(which is an all silicon zeolite).[29] No other peaks have
developed frem the formation of Al-OSi bonds by the reaction of
aluminum chloride. The aluminum chloride has simply been hydrolyzed
and for the most part is a weakly associated 6-coordinate species on
the SiC>2 surface. The slight broadening of the 29Si peak compared
to unmodified Si02 could be the result of weak association with
these aluminum species. Another factor that will contribute to the
peak broadening is that not all silicons are bonded together by
oxygen bridges (Si-O-Si) in silica gel. On the surface of the
silica gel the silicon dioxide lattice terminates in Si-O-H
(silanol) groups whose chemical shift is approximately 1 ppm
different from that of groups in the bulk lattice.[29]
The next material examined was a catalyst which had been
prepared by refluxing Si02 and A12C16 in dry CC14 under an N2


46
150
Figure 2-11.
An 27Al Solid-State NMR of an AlCl^i-SiC^ Catalyst
Prepared in the Presence of H20.
PFM


47
Figure 2-12. A 29Si Solid-State NMR of an AlCl2-SiC>2 Catalyst
Prepared in the Presence of H20.


48
atmosphere. The 27Al MAS NMR for an active catalyst (before
catalysis) is shewn in Figure 2-13. The peak at 0 ppm results from
the presence of 6-coordinate aluminum which formed after the
catalyst was exposed to water vapor in the air during the loading of
the NMR tube. The peak centered at 55 ppm results from 4-coordinate
aluminum, most likely with hydroxide ligands as well as Al-O-Si
bonds. The peak at 55 ppm could also arise from the formation of
zeolitic aluminum by addition of aluminum into a surface vacancy as
shewn in Equation 2-10.[33]
Si Si
O 0
H H1"
2 SiOH HOSi + A12C16 > 2 SiO Al OSi + 6 HCl (2-10)
H
O O
Si Si
The peak at 65 ppm results from Si-0-AlCl2 on the silica gel
surface which would be consistent with the value of 62.8 ppm given
for aluminum chlorohydrate with a ratio of Cl/OH of 2.5.[31]
When a high surface area silica gel is treated with aluminum
chloride several types of tetrahedral aluminum centers are formed.
Shown in Figure 2-14 is the 27A1 MAS NMR for a 690 n^/gram silica
gel treated with aluminum chloride. For the high surface area
silica gel three distinct peaks are detected which are at 70, 52 and
23 ppm. The peak at 70 is assigned to a Si-0-AlCl2 species which
was observed for the 340 m2/gram silica gel. The peak at 52 ppm
most likely results frem zeolitic or hydroxychloro [Si-O-AlCl(OH)]


49
i i ' ' i ' ' i ' ' I 1 l ' ¡ ' l
150 100 50 0 -50 -ICO -150 -200
Figure 2-13. An 27A1 Solid-State NMR of an Active AlCl2-Si02
Catalyst Prepared in the Absence of H20.


50
aluminum centers and the peak at 23 ppm probably results from a
chemisorbed 6-coordinate hydroxy chi oro aluminum species.
This may be explained using the stoichiometry of the catalyst
preparation reaction. The aluminum chloride treated silica gel is
normally prepared using a silica with a surface area of 340 m2/gram
and a hydroxyl group concentration of approximately 10
mmole/gram. [35,47] Since a 2:1 ratio by weight of inorganic oxide
to aluminum chloride is used there are 7.5 mmole of AICI3 per gram
of support which would yield roughly 80% coverage of the solid
support. If the surface area of the support is doubled a
corresponding increase in the concentration of hydroxyl groups would
occur and the total coverage of the aluminum chloride would decrease
to approximately 40%. This would mean that there would be, on
average, 2.5 hydroxyl groups for every AICI3 molecule used in the
reaction. According to this stoichiometry an average of two Al-Cl
bonds would be hydrolyzed by the silica surface for every AICI3
molecule used in the reaction. The resulting 27A1 MAS NMR should
then shew a significant increase in the number of bands for
hydrolyzed chloroaluminum species as in Figure 2-14.
Shewn in Figure 2-15 is the 29Si MAS NMR of the 690 m2/gram
silica gel reacted with aluminum chloride in CC14. In contrast to
Figure 2-12 where only one peak was observed for the 29Si MAS NMR,
there are new at least two distinct peaks centered at -88 and -105
ppm. The peak at -105 ppm is due to the formation of one Si-O-Al
bond per silicon atom on the silica surface and the peak at -88 ppm


51
Figure 2-14. An 27A1 Solid-State NMR of an AlCl2-SiC>2 Catalyst
Prepared with a 690 xt^/gram Surface Area Silica
Gel.


52
A 29Si Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared with a 690 n^/gram Surface Area Silica
Gel.
PPM
Figure 2-15.


53
is due to the formation of two Si-O-Al bonds to one silicon center
on the silica surface. These results are consistent with literature
values given for amorphous silica-aluminas, aluminosilicates and
zeolites.[29,30]
The presence of peaks ar -88 and -105 ppm are good evidence for
the incorporation of aluminum chloride onto the silica surface and
supports the fact that the aluminum chloride has actually been
chemically bonded to the solid support. When the catalysts studied
in Figures 2-14 and 2-15 are used in a catalytic cracking reaction
(reported later in this section) lew activities are observed. This
may be the result of the increased amount of hydrolyzed
chloroaluminum centers present on the catalyst surface. The
activity that is observed may result from a lew number of hydroxy
chloro species and zeolitic aluminum centers which would only show
high activities at high temperatures.[2,3]
The 27A1 and 29Si MAS NMR spectra of a silica gel support which
has been treated with excess Al2Cl6 (100 wt%) is shewn in Figures 2-
16 and 2-17. For the 27A1 MAS NMR a large peak at 105 ppm is
observed which results from unccmplexed aluminum chloride and is in
agreement with the shifts reported in the literature for the 27A1
solution NMR of Al2Clg and A1C14. [32] Peaks in the 27A1 MAS NMR
are also observed at 38 and 0 ppm which result from the
hydroxychloro aluminum species discussed earlier. The 29Si MAS NMR
spectrum of the same catalyst exhibits only one peak, resulting from
the framework silicon dioxide [29], indicating that most of the
aluminum chloride is on the support surface as A12C16.


54
150 100 50 0 -50 -100 -150 -200
Figure 2-16. An 27A1 Solid-State NMR of an AlCl2-SiO? Catalyst
Prepared with 100 wt% of Aluminum Chloride.
PM


55
Figure 2-17. A 29Si Solid-State NMR of an AlCl2-Si02 Catalyst
Prepared with 100 wt% of Aluminum Chloride.
PPM


56
The 27Al and 29Si MAS NMR spectra of a catalyst after use in a
catalytic cracking reaction are shewn in Figures 2-18 and 2-19.
Once again in the 27A1 MAS NMR 6-coordinate and 4-coordinate
aluminum centers are present with the 4-coordinate aluminum center
giving a peak at -70 ppm which would indicate the presence of an Si-
0-AlCl2 species. The oscillation in the 27A1 MAS NMR baseline is
caused by seme paramagnetic material (coke) which was deposited on
the catalyst surface during catalysis. The 29Si MAS NMR displays
peaks for the framework silicon dioxide plus the silicon atoms
associated with the formation of one Si-O-Al bond per silicon
center. This indicates that even under catalytic conditions the
tetrahedral chloroaluminum centers are stable and could be
responsible for the catalytically active centers.
From the 27A1 and 29Si MAS NMR data it has been determined that
the catalyst prepared by reaction of aluminum chloride with
aninorganic oxide results in a solid material which has tetrahedral
chloroaluminum centers. The IR data for adsorbed pyridine indicates
that both Bronsted and Lewis acid sites are present and the
frequency shifts for the Lewis acid bound pyridine are comparable to
those exhibited by conventional cracking catalysts. [16,17] As a
result of these findings the new solid acid catalysts described in
the experimental section of this chapter were used for various
hydrocarbon conversion reactions.
The next section will deal with the characterization of the
radical on the catalyst surface generated during the catalyst


57
Dm
4 I I
Figure 2-18. An 27A1 Solid-State NMR of an AlCl2-Si02 Catalyst
After Reaction with n-Fentane.


58
Figure 2-19. A 29Si Solid-State NMR of an AlCl2-Si02 Catalyst
After Reaction with n-Fentane.
PPM


59
preparation. The following sections will discuss the solid acids
use as catalytic cracking and polymerization catalysts.
Characterization of the Radical on the Catalyst Surface
It was reported in the experimental section that when the
inorganic oxides treated with aluminum chloride are prepared in
refluxing solvents a free-radical species is formed on the solid
materials with a g value of 2.012. No hyperfine splitting is
observed for the radical signal even at 4 K. In order to identify
the radical species present magnetic susceptibility measurements and
spin trapping experiments have been conducted on the aluminum
ciiloride treated silicon dioxide made in carbon tetrachloride.
The procedure for the spin trapping experiments using the
diamagnetic spin trapping agent EMPO are outlined in the
experimental section of this chapter. Whenever the radical was spin
trapped in carbon tetrachloride no change in the radical signal was
observed indicating that the radical on the surface was not a very
reactive species. If the radical is spin trapped in toluene a
radical is trapped which has the EER spectrum shewn in Figure 2-20.
The signal obtained had a g value of 2.0152 with an observed
nitrogen hyperfine splitting constant of 14.225 gauss and a beta
hydrogen hyperfine splitting constant of 20.275 gauss. The
simulated EFR spectrum shown in Figure 2-21 was obtained using an
EER simulation program as modified by J. Telser. [38-40] When the
hyperfine splitting constants obtained from the spectrum in Figure
2-20 are compared to literature values[48,49] of known spin trapped


60
an aN
2300
B/Gauss
I
3300
4300
Figure 2-20. Radical on AlCl2Si02 Spin Trapped Using EMPO
in Toluene.


61
Figure 2-21. EFR Simulation of Radical on AlCl2-SiC>2.


62
radicals with EMPO, it is found that the EER spectrum of Figure 2-
20 is for the benzyl radical and not the radical on the surface of
the catalyst. These results suggest that the radical on the surface
is delocalized by the inorganic oxide matrix resulting in a
relatively stable free-radical which is not capable of being spin
trapped by EMPO.
It has been reported in the literature that compounds such as
Al2Clg act as one-electron oxidizing agents towards electron rich
substrates.[43,50,51] A solution of aluminum chloride and
dichloromethane is capable of oxidizing any substrate which has a
first (adiabatic) ionization energy belcw 8 eV. The first
ionization energies for all the solvents used to prepare the
catalyst are well above 8 eV[52] which suggests that the radicals
are not derived iron the one-electron oxidation of solvent molecules
which are then adsorbed onto the catalyst surface. Since the first
ionization energies for the elements silicon, aluminum, titanium,
magnesium and boron are 8.3 eV[46,52,53] it is reasonable to
suggest that the radical is derived from the one-electron oxidation
of the support. The radical species generated on the support are
delocalized throughout the inorganic oxide matrix causing the
radical to be unreactive. Because the EER spectrum of the radical
species on aluminum chloride treated silica gel made in refluxing
carbon tetrachloride shews no hyperfine splitting even at 4 K the
radical is most likely oxygen based. The inability to spin trap the
radical, the absence of any radical chemistry in the cracking of
hydrocarbons and the absence of radical initiated polymerizations


63
all support the idea of delocalized radical species on the catalyst
surface. The radical chemistry in the cracking of hydrocarbons and
the radical initiated polymerizations will be discussed later in
this chapter.
Our catalyst is prepared by the reaction of silica gel with
aluminum chloride in a 2:1 ratio by weight. This corresponds to a
4.4:1 mole ratio of silica gel to aluminum chloride. Using this
ratio we have calculated a formula weight of 3977.1 grams/mole
corresponding to a formula unit of S440g8Al10cl20* 11116 catalysts
sent for magnetic susceptibility measurements [ 54 ] were the catalysts
prepared in carbon tetrachloride and benzene. For the catalyst made
in carbon tetrachloride there were 0.246 unpaired electrons per
formula unit and the catalyst made in benzene had 0.289 unpaired
electrons per formula unit. A second batch of catalyst made in
benzene had 0.142 unpaired electrons per formula unit indicating
that the radicals are not very concentrated and that the radical
concentration does not change significantly when the catalyst
preparation is changed. This also indicates that the radical
concentration does not correlate with catalytic activity. The
catalyst prepared in carbon tetrachloride is a very active acid
cracking catalyst and the catalyst prepared in benzene is about 5
orders of magnitude lower in activity; however, the number of
unpaired electrons per formula unit is approximately the same. The
radical concentration does not correlate with the catalytic activity
of the catalysts.


64
Titration of Strong Acid Sites with Pyridine
A series of calorimetric titrations in addition to the infrared
and NMR studies were performed on several of the solid acid
catalysts. The purpose of the titrations was to measure the
enthalpy of binding of pyridine to the acid sites present on the
catalyst surface. Pyridine was used as the titrant and the
procedure was the same as previously described in the
1iterature.[55-57]
The first material titrated was the catalyst prepared by
refluxing SiC>2 and A12C16 in dry CC14 under an N2 atmosphere.
Results from the titrations indicated that the enthalpy of binding
of pyridine to the first 13.6% of the surface acid sites ranged from
48.2 Kcal/mole to 17.1 Kcal/mole. The average enthalpy of binding
measured for the acid sites titrated was 36.0 Kcal/mole. This value
is consistent with the values reported in the literature by other
workers for amorphous silica-alumina, aluminosilicates and
zeolites.[17,18]
The second material was a catalyst prepared by refluxing a
palladium chloride doped silica gel and aluminum chloride in CC14
under an N2 atmosphere. Results from the titrations indicated that
the enthalpy of binding from the first 11.8% of the surface sites
ranged from 45.0 Kcal/mole to 23.9 Kcal/mole. The average enthalpy
of binding measured for the acid sites titrated was 36.5 Kcal/mole.
This indicates that the strength of the acid sites on the catalyst
are not affected by the addition of a metal chloride. This finding
is in agreement with a report in the literature on a palladium


65
loaded zeolite. [22] Additional work is being conducted on the
titration of the solid acids and will be reported in the future. [58]
Catalytic Cracking of Hydrocarbons by a New Solid Acid Catalyst
System
The preparation and use of strong acid catalysts and superacids
are active areas of research for isomerization, cracking,
hydrocracking, dehydration, alkylation, acylation, polymerization,
conversion of methanol to gasoline, and so forth.[6] Because of the
reported advantages of solid acids,[5] recent research has been
focused on the preparation and characterization of stronger solid
acids. In view of the higher acidities associated with tetrahedral
compared to octahedral aluminum Lewis acids, solid acid catalysts
were prepared containing stable tetrahedral aluminum sites. Since
one of the largest uses of solid acid catalysts is in the area of
catalytic cracking[2,3,59], the solid materials prepared in the
experimental section of this chapter were used for various catalytic
cracking reactions in both gas-solid flew reactors and liquid-solid
batch reactors.
Reaction of a Silica Gel Treated with Aluminum Chloride and Various
Straight Chain Hydrocarbons in a Fixed Bed Flow Reactor
The initial experiments for the cracking of hydrocarbons were
performed using a fixed bed flew reactor as described in the
experimental section of this chapter.
The first reaction conducted was the cracking of n-pentane with
an AlCl2-Si02 catalyst prepared in CC14. Represented in Figure 2-22


66
is a GC chromatogram of the effluent gas from the reaction of n-
pentane, HC1 and hydrogen in a 2.5:4:1 ratio by volume with a flow
rate of 1 ml/17 sec at 175C. Products were trapped at -78C using
a Dry Ice-acetone bath and samples were taken using a gas-tight
syringe. At this flew rate the ratio of methane, prepane,
isobutane, n-butane and isopentane to n-pentane is lew and
corresponds to less than 15% conversion. If the flew rate is slowed
by a factor of 2 so that the residence time of the reactants on the
catalyst is doubled a marked increase in the percent conversion is
observed, Figure 2-23. The increased conversion upon increasing the
residence time of the reactants with the catalyst is not unexpected
and is a ccranon phenomenon of fixed bed flew reactors. An activity
curve for the reaction an AlCl2-SiC>2 catalyst with n-pentane is
shewn in Figure 2-24. During the progress of the catalytic reaction
there is an initial increase in activity which is followed by a
decrease in activity of up to three orders in magnitude. After
approximately 8 hours the catalyst reaches a near steady-state
activity which decreases slowly with time. The activity of the
catalyst is similar to other cracking catalysts that are reported in
the literature.[2,3] The initial activity can be explained by the
presence of a few highly acidic sites on the catalyst which exhibit
high activity but rapidly deactivate from coke formation. After the
initial surge in activity the less acidic site exhibit a lower
activity for cracking and a lower rate of coke formation which
causes the activity to remain almost constant with time. The
activity of these less acidic sites decrease with time and,


67
Figure 2-22. GC Chromatogram from the Reaction of n-Pentane
with a Solid Acid Catalyst at Fast Flew Rates.


68
Figure 2-23. GC Chranatogram fren the Reaction of n-Pentane
with a Solid Acid Catalyst at Slew Flew Rates.


MOLES PRODUCT x¡0-
HR MOLES METAL
69
Figure 2-24. Activity Curves for the Reaction of n-Pentane with
a Solid Acid Catalyst at 175C.


70
after 24 hours with n-pentane as the feed, the catalyst exhibits
only minimal activity for cracking.
Hie activation energy for the cracking of n-pentane is greater
than 36.6 Kcal/mole which favors the formation of coke.[2,3] As the
chain length of the hydrocarbon is increased, the activation energy
required to crack the hydrocarbon decreases with increase in the
rate of reaction and decrease in the amount of coke formation. The
activation energy for n-heptane is 29.4 Kcal/mole and n-octane has
an activation energy of 24.9 Kcal/mole. [3] For hydrocarbons with
chain lengths longer than 8 carbons the activation energy does not
decrease significantly belcw that of n-octane. [3]
The next substrate to be used for a cracking reaction was n-
heptane. This was to demonstrate that using a longer chain
hydrocarbon would increase the activity and the lifetime of the
catalyst over what was exhibited for n-pentane. The reaction of n-
heptane, HC1 and hydrogen in a 1:4:0.1 ratio by volume was conducted
at 175C in a fixed bed flew reactor. Products were collected at -
78 C using a Dry Ice-acetone bath and identified by GC and GC/MS.
Figure 2-25 represents a GC chromatogram for the cracking of n-
heptane by an AlCl2-Si02 solid acid catalyst prepared in CC14. The
mass spectra of the products from the reaction of n-heptane with an
AlCl2-Si02 solid acid catalyst are shewn in Figures 2-26 to 2-30.
The major products of this reaction are prepane, isobutane and n-
butane with minor amounts of n-pentane, isopentane, ethane and
methane being produced. In addition to the products listed above,
trace quantities of 2-methylhexane were detected by GC/MS as a


71
product of the reaction and no other products were detected. An
activity curve for the cracking of n-heptane by an AlCl2-Si02
catalyst prepared in CC14 is shewn in Figure 2-31. The activity
curve for n-heptane is similar to the activity curve for n-pentane
and shews that the catalyst exhibits the same catalytic behavior for
the two hydrocarbon substrates. The catalyst used in the cracking
of n-heptane exhibits an increase in catalyst activity for 10 hours
and still shews considerable activity after 90 hours of reaction.
The longer time required to reach a near steady-state production of
products front n-heptane most likely results from the lower vapor
pressure of n-heptane compared to n-pentane which leads to a lower
feed rate.
A simplified scheme for the cracking of n-heptane into the
major products (propane, isobutane, and n-butane) is shown in Figure
2-32. In this scheme only reactions that proceed to the formation
of products are represented. The first step is the abstraction of a
hydride ion from the hydrocarbon to form a secondary carbonium ion.
The next step is methide and hydride migration to form a more stable
tertiary carbonium ion. After a subsequent 2 step hydride migration
the iscmerized heptane carbonium ion undergoes a 13-scission to
formh-butene and the propyl carbonium ion. The propyl carbonium ion
can abstract a hydride ion from a substrate molecule to propagate
the reaction and form propane which is a major product of the
reaction. If the propyl carbonium ion losses a proton, propylene
will be formed which in the presence of Bronsted acid


72
products collected at -78C
d
Figure 2-25. GC Chromatogram from the Reaction of n-Heptane
with a Solid Acid Catalyst at 175C.


73
Observed Spectrum
100 29
Reference Spectrum60
PROPANE
44.06260 CO MB AA-10*3
_jJ
zo
U-4-x
40 60 80 100 120 140 ISO
. 1 . 1
Figure 2-26. Mass Intensity Report for Prepane.


74
Reference Spectrum60
100
80
so
40
20
0
1
2 metkylpropane c i soetn ane )
58.07825
C4 HI0 AA33*2
Jj
20 40 SO 80 100 120 140 1 SO '
U-,1l*+*.... ,
Figure 2-27. Mass Intensity Report for Isobutane


75
43 Observed Spectrum
Reference Spectrum60
N-BUTANE
S8.Q70ZS C4 H10 AA* 31*3
Figure 2-28. Mass Intensity Report for n-Butane


76
Observed Spectrum
Reference Spectrum60
100
BO
so
40
zo
0
1
2-uethvlbutanensopentanei
72.03390 CS M12 AA-74-S
JL
L
20 40 SO 80 100 120 140 ISO
Figure 2-29. Mass Intensity Report for Iscpentane


77
Observed Spectrum
Reference Spectrum60
100
BO
BO
40
20
20 40 SO 80 100 120 140 ISO
1- i
N-PENTANE
22.09090 CS HI2
AA-7S-1
Figure 2-30. Mass Intensity Report for n-Pentane


78
X = PROPANE
O = ISO BUTANE
Figure 2-31. Activity Curves for the Reaction of n-Heptane with
a Solid Acid Catalyst at 175C.


Figure 2-32. A Siirplified Scheme for the Cracking of n-Heptane.


80
CH3CHHCH2CH2CH2CH3
0 'T
CH CCH^H CH^H
h3
I. CHj MIGRATION
2.H: MIGRATION
2 STEP.H: MIGRATION
^
c^cH
1 I J
R I \RH


81
sites on the catalyst surface will be reprotonated and reenter the
reaction scheme.
The n-butene formed from the 6-scission of the n-heptane
carbonium ion could be protonated by a Bronsted acid site to form a
secondary butyl carbonium ion. The butyl carbonium ion can then
abstract a hydride ion from a substrate molecule to form n-butane
which is one of the major products. The secondary butyl carbonium
ion may also undergo a methyl and hydride migration to form the
isobutyl carbonium ion which will abstract a hydride ion to form
isobutane.
All of the reaction steps depicted in the simplified scheme are
well documented in the literature and are generally accepted as
steps in cracking catalysis. An in depth study of the various
reactions that can occur during cracking reactions is outside the
scope of this dissertation and detailed reviews of this chemistry
may be found in the literature.[2,3,42,44]
Many other reactions may occur simultaneously such as
polymerization reactions involving the reaction of olefins with
carbonium ions to form high molecular weight hydrocarbons that may
be recracked to smaller hydrocarbons. It was indicated in the
reaction scheme that hydride abstraction from substrate molecules is
a facile reaction. This hydride ion abstraction from hydrocarbon
substrate molecules is the source of coke formation which is the
leading cause of catalyst deactivation for catalytic reactions
involving solid acid catalysts. [2,3] The formation of coke is
initiated by adsorption of a hydrocarbon molecule onto the catalyst


82
surface followed by rapid hydride ion abstraction to form a highly
unsaturated hydrocarbon with a low H/C ratio which can no longer
desorb fren the catalyst surface. [3] This adsorbed hydrocarbon
molecule eventually will form a polymeric film that will cover the
surface of the catalyst blocking the active centers and deactivating
the catalyst.[2]
If the reactions of various hydrocarbons are conducted with
carbon tetrachloride as the chlorine source in place of hydrogen
VxaJT
chloride the same catalyst selectivity is observed, when the
catalyst exhibits a greater stability and a longer lifetime when
carbon tetrachloride is used as the chlorine source. Since the
catalyst is prepared in carbon tetrachloride an increase in catalyst
stability should result when it is used as a chlorine source. There
are several reasons why the use of CC14 as a chlorine source may
lead to greater catalyst stability. One reason may be that CC14
stabilizes the aluminum-chlorine bonds on the catalyst in the same
manner described in the catalyst preparation section. Another
reason may be that CC14 regenerates the catalytically active species
which is deactivated when the catalyst abstracts a hydride ion from
a hydrocarbon substrate.
When carbon tetrachloride is used as the chlorine source
hydrogen chloride and chloroform are detected in the product stream.
The amount of chloroform generated in the reaction is of the same
order of magnitude as the amount of substrate cracked. With this
information a mechanism for the catalytic cracking of hydrocarbons


83
in the presence of 0C14 can be proposed and is presented in Figure
2-33.
It is generally accepted that the cracking of hydrocarbons
proceeds via the generation of carbonium ions through the
protonation of alkenes by Bronsted acid or hydride ion abstraction
from saturated hydrocarbons with Lewis acids. [2,3] In the mechanism
proposed in Figure 2-33 the Bronsted acid sites are not depicted
because they are not crucial to the catalytic cycle.
The first step in the reaction would be the abstraction of a
hydride ion and the generation of an alkyl carbonium ion. During
this reaction the chloroaluminum species would accept the hydride
ion and decrease the interaction between the lone pair of the
bridging oxygen and the aluminum. The chloroaluminum hydride
species formed would have to be regenerated to the starting
chloroaluminum species to make the process catalytic.
The process of regenerating the active center could be started
by attack of carbon tetrachloride on the chloroaluminum center to
generate a species analogous with CljCtAlCl,*- which is reported to
form upon reaction of aluminum chloride and carbon
tetrachloride. [42-44] This species could then dissociate into a
djC* carbonium ion and a support-O-AlCl 3 ~ anion. The C13C+'
carbonium ion then may abstract a hydride ion frcm a substrate
molecule propagating the cracking reaction and forming chloroform
which is observed in the productstream. Another path the
carbonium ion may take is abstraction of the hydride from the
chloroaluminum hydride to reform the active catalytic center.


Figure 2-32. A Simplified Scheme for the Cracking of n-Heptane.


Full Text
UNIVERSITY OF FLORIDA
3 1262 08554 2834


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