Catalysis, Vol. 19

265 Pages·2006·5.734 MB·English

by  James J Spivey, Justin Hargreaves, James G Goodwin

Catalysis
Volume 19

A Specialist Periodical Report
Catalysis
Volume 19
A Review of Recent Literature
Editors
J.J. Spivey, Louisiana State University, Baton Rouge, USA
K.M. Dooley, Louisiana State University, Baton Rouge, USA
Authors
David A Berry, US Department of Energy, West Virginia, USA
David A Bruce, Clemson University, South Carolina, USA
TV Choudhary, ConocoPhillips Company, Bartlesville, USA
Todd H Gardner, US Department of Energy, West Virginia, USA
DW Goodman, Texas A&M University, Texas, USA
James G Goodwin Jr, Clemson University, South Carolina, USA
JSJ Hargreaves, University of Glasgow, UK
CGM Hermse, Eindhoven University of Technology, The Netherlands
APJ Jansen, Eindhoven University of Technology, The Netherlands
Yijun Liu, Clemson University, South Carolina, USA
Dora E Lopez, Clemson University, South Carolina, USA
Edgar Lotero, Clemson University, South Carolina, USA
D McKay, University of Glasgow, UK
Fernando Morales, Utrecht University, The Netherlands
Dushyant Shekhawat, US Department of Energy, West Virginia, USA
Kaewta Suwannakarn, Clemson University, South Carolina, USA
Bert M Weckhuysen, Utrecht University, The Netherlands
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ISBN-10:0-85404-239-3
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ISSN0140-0568
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Preface
Catalysiscontinues tobeastrong andengaging areaofresearch.Newtools
are being used to explore the complex processes taking place at the catalyst
surface.Conversion ofbothtraditionalandnew fuels tomeetthe challenge of
clean energy is becoming more important. The reviews in this volume address
these topics.
JimGoodwin,Jr.andcolleaguesatClemsonUniversity(EdgarLotero,David
Bruce, and Kaewta Suwannakarn, Yijun Liu, and Dora Lopez) review the
application of solid acid catalysts for the synthesis of biodiesel from renewable
sources. Biodiesel is produced by the acid-catalyzed esterification of fatty acids
derivedfromrenewablessuchasvegetableoil.Althoughthisesterificationcanbe
carriedoutusinghomogeneousacidcatalysts,thereareclearprocessadvantages
tousingheterogeneouscatalysts—providedthenecessaryactivityandselectivity
canbeachieved.Theauthorsassessboththecurrentprocessesthatarebasedon
homogeneous catalysts, as well as recent studies of heterogeneous catalysts,
which havenot been extensivelyreviewedtodate.
Nitridesandoxynitridesrepresentarelativelynewclassofcatalyticmaterial.
JustinHargreavesandD.McKay(UniversityofGlasgow,UK)showthatthese
materials have only recently been explored for reactions (e.g., photocatalysis)
beyondthosethattakeadvantageoftheiracid-basepropertiesandtheirability
to mimic Pt-based catalysts. Tuning the acid-base properties of nitrides is
possible by incorporating oxygen within their structure.
Cobalt-basedFischer-Tropschcatalystsarethesubjectofcontinuinginterest
aslarge-scaleGas-to-Liquidsplantscomeonline.FernandoMoralesandBert
Weckhuysen (Utrecht University, the Netherlands) look specifically at the
effects of various promoters for these catalysts, particularly Mn. The effect of
thesepromotersincontrollingtheactivityandselectivityoftheoverallreaction
canbecriticalintheoverallprocesseconomics.Thischapteralsolooksatnew
spectroscopic techniques that have recently been used to study the effects of
these promoters.
The decomposition of methane isan important process since it can produce
two valuable products: hydrogen and carbon filaments. Wayne Goodman
(Texas A&M University) and Tushar Choudhary (ConocoPhillips) show that
methane decomposition may be a viable alternative to conventional steam
reforming as a source of hydrogen, without the formation of CO as a
x
byproduct.Theauthorsexaminetheeffectsofcatalystsupportandpromoters,
as well as the inevitable regeneration of the catalyst. The formation of carbon
fibers, under certain conditions, makes this process an attractive one.
v
vi Catalysis,2006,19,v–vi
Another route to hydrogen for fuel cell energy applications is the catalytic
reformingofliquidfuels.InareviewbyauthorsfromtheUSDept.ofEnergy
(Dushyant Shekhawat, Dave Berry, and Todd Gardner) and Louisiana State
University (Jerry Spivey), the catalysts used for this reaction are examined.
Among the key issues in this process are carbon deposition and sulfur
poisoning. These deactivation mechanisms are widely recognized as barriers
to the widespread use of catalytic reforming. The kinetics of the complex
reformingprocess,whichincludespartialoxidation,steamreforming,andshift
reactions, are also reviewed.
Finally, the application of computational methods to the study of catalysis
continues to increase dramatically. C.G.M. Hermse and A.P.J. Jensen (Eind-
hoven University of Technology, the Netherlands) present a review of the
kinetics of surface reactions with lateral interactions. These methods can be
used in predicting catalytic reaction mechanisms. In particular, the authors
discusstheroleoflateralinteractionsinadsorbedlayersatequilibriumandthe
determination of lateral interactions from experiments—using the simulations
to interpret experimental results. This chapter illustrates the increasing use of
computational methods to understand and to design catalysts.
I welcome to this volume my Co-Editor and colleague at Louisiana State
University, Kerry Dooley. He is well-known to many in the catalysis commu-
nityforhisresearchinacid-basecatalysis.Amongotherresponsibilities,hewill
serveasMeetingCo-ChairfortheupcomingNorthAmericanCatalysisSociety
meeting, to take place in Houston on June 17–22, 2007.
As always, comments are welcome.
James J. Spivey
Gordon A. and Mary Cain Dept. Chemical Engineering
Louisiana State University
Baton Rouge, LA 70803
[email protected]
Kerry M. Dooley
Gordon A. and Mary Cain Dept. Chemical Engineering
Louisiana State University
Baton Rouge, LA 70803
[email protected]
Contents
Cover
Imageprovidedcourtesy
ofcomputationalscience
companyAccelrys
(www.accelrys.com).An
electrondensityisosurface
mappedwiththeelectrostatic
potentialforanorganometallic
molecule.Thisshowsthe
chargedistributionacrossthe
surfaceofthemoleculewith
theredareashowingthe
positivechargeassociatedwith
thecentralmetalatom.
Researchcarriedoutusing
Accelrys’MaterialsStudios.
Promotion Effects in Co-based Fischer-Tropsch Catalysis 1
Fernando Morales and Bert M. Weckhuysen
1 General Introduction 1
1.1 Fischer-Tropsch Synthesis 1
1.2 Scope of the Review Paper 5
2 Fischer-Tropsch Catalysis 6
2.1 Gas-to-Liquid Technology, Economic Impact and its
Relevance to Society 6
2.2 Fischer-Tropsch Catalysts 8
3 Co-based Fischer-Tropsch Catalysts 9
3.1 Promotion Effects 10
3.2 Overview of the Promoter Elements Used in
Co-based F-T Catalysts 16
4 Mn-promoted Fischer-Tropsch Catalysts 21
4.1 Mn-promoted Fe-based Fischer-Tropsch Catalysts 22
5 Concluding Remarks and Outlook 30
6 Acknowledgments 32
References 32
vii
viii Catalysis,2006,19,vii–x
The Catalysis of Biodiesel Synthesis 41
Edgar Lotero, James G. Goodwin, Jr., David A. Bruce,
Kaewta Suwannakarn, Yijun Liu and Dora E. Lopez
1 Introduction 41
2 Overview 43
2.1 Vegetable Oils and Animal Fats 43
2.2 Reactions 44
2.3 Physicochemical Properties of Biodiesel 46
2.4 The Feedstock Issue 47
2.5 Processing Methodologies 48
3 Homogeneous Catalysis 49
3.1 Base-Catalyzed Synthesis 49
3.2 Acid-Catalyzed Synthesis 55
3.3 Integrated Acid-Base Biodiesel Synthesis 60
3.4 Existing Problems with Homogeneous Catalysts 62
4 Heterogeneous Catalysis in Biodiesel Synthesis 63
4.1 Catalysis by Metals, Metal Compounds and
Supported Metal Complexes 64
4.2 Catalysis by Solid Bases 67
4.3 Catalysis by Solid Acids 72
4.4 Potential Problems with Heterogeneous
Catalysts 77
5 Conclusions and Future Perspectives 78
References 80
Catalysis with Nitrides and Oxynitrides 84
J.S.J. Hargreaves and D. Mckay
1 Introduction 84
2 Preparation of Nitride and Oxynitride Catalysts 85
3 Catalytic Reactions with Nitrides and Oxynitrides 89
3.1 Ammonia Synthesis, Ammonia Decomposition
and Hydrazine Decomposition 89
3.2 Amination and Ammoxidation 92
3.3 NO Removal 93
3.4 Hydrotreating and Hydrogenation 94
3.5 Base Catalysis 96
3.6 Photocatalysis 98
3.7 Use as Supports 99
Catalysis,2006,19,vii–x ix
3.8 Hydrogen Storage 102
4 Conclusions and Outlook 102
5 Acknowledgments 103
References 103
Kinetics of Surface Reactions with Lateral Interactions: Theory and
Simulations 109
C.G.M. Hermse and A.P.J. Jansen
1 Introduction 109
2 Basics of Lateral Interactions 110
2.1 The Mechanism of Lateral Interactions 110
2.2 Equilibrium Aspects 114
2.3 Effect of Lateral Interactions on the Kinetics 119
3 Theory 120
3.1 Including Lateral Interactions in the Kinetics 121
3.2 Analytical Expressions for Lateral Interactions 133
3.3 Experimental Determination 135
3.4 Calculating Lateral Interactions 137
4 Examples 143
4.1 NO/Rh(111) 143
4.2 Sulfate on Fcc(111) Surfaces 145
4.3 CO/Rh(100) 148
4.4 O/Pt(111) 151
4.5 Tartaric Acid on Cu(110) 153
5 Outlook 155
6. Acknowledgments 157
References 157
Methane Decomposition: Production of Hydrogen and
Carbon Filaments 164
T.V. Choudhary and D.W. Goodman
1 Introduction 164
2 Hydrogen Production 166
2.1 Catalytic Decomposition of Methane for
Hydrogen Production 166
2.2 Step-wise Methane Reforming: Regeneration
Issues 172