University of Alberta One-step Oxidation of Propylene to Acrylic Acid Sachindra Sood A thesis ...

97 Pages·1998·4.54 MB·English

University of Alberta
One-step Oxidation of Propylene to Acrylic Acid
Sachindra Sood O
A thesis submitted to the Faculty of Graduate Studies and Research
in partial fulfillment of the requirements for the degree
of Master of Science
Department of Chernical Engineering
Edmonton, Alberta
FaIl 1995
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This thesis is dedicated to
Brahmachari Sant Chaitanya
Abstract
This thesis is primariiy concemed with the development of a catalytic process for the
single step oxidation of propylene to acrytic acid. The process employs palladium catalyst
irnpregnated on polymeric hydrophobic supports. These cataiysts display promising
reactivity and selectivity towards the desired product. The hydrophobicity of these
catalysts plays an important role in the marked improvement of their activiv over similar
catalysts supported on conventional supports. In the course of process developrnent, the
controiling effect of various parameters like metal loading, cataiyst composition, feed
composition, pressure and temperature are atso studied, with a view to optimize operating
conditions for the process. However, these catalysts failed to stand up to the test of long
term stability, deactivating under the conditions of use. This loss in activity is believed to
have been caused by a product contaminant, possibly a polymer of acryiic acid.
Acknowledgments
I am extremely gratefiil to Dr. KT. Chuang for his technical advice and personal guidance
during this work. In discussions and conversations, he gave generously of his tirne and
expertise.
Special thanks are due to Dr. Bing Zhou for the flawless operation of the experirnental
equipment and his technical support in practîcally all aspects of this work, and to Dr.
Stefm Slavov for his help d u ~thge writing of this thesis. 1 also express my gratitude to
Walter Boddez for the ingenuity displayed in getting the iiquid chromatograph to perfect
working condition. 1 am especially thankfiil to Dr. Ramesh Sadhankar for sharing his
knowledge with me, and pointing out several finer points of academic penmanship.
I appreciate the cherished companionship of several fiends and colleagues who
contributed in making Me as a graduate student rnuch more enjoyable.
Financial support from the Department of Chernical Engineering and the Natural Sciences
and Engineering Research Council of Canada is gratefully acknowledged.
Above ail, 1 would like to express my sincerest gratitude to my parents for their
unconditional love and support throughout my We regardless of what endeavor 1 was
involved in.
Contents
Introduction
Literature Review 5
Manufacture of acrylic acid ..................................................................... -5
Commercial routes of the past ................................................................. -6
Other syntheses ....................................................................................... -9
Manufacture of acrylic acid fiom propylene ............................................ 10
Liquid phase oxidation of propylene. ..................................................... -14
Liquid phase oxidation of acroiein .......................................................... 15
Liquid phase oxidation of propylene to acrylic acid over
Ni or Mn catalyst ................................................................................. 15
Role of palladium in olefenic oxidation. .................................................. 16
Liquid phase oxidation of propylene
using palladium catalyst. ......................................................................... 17
Chemistry of the process of propylene oxidation. .................................... 19
Catalyst Preparation and Characterization 22
3.1 Selection of catalyst support ................................................................... 22
3.2 Catalyst Preparation. ............................................................................. -26
3.2.1 Pd/SDB ...................................................................................... 27
3.2.2 Pd-Pt/SDB, Pd-Ir/SDB, Pd-Ru/SDB .......................................... -28
Experimental Setup and Procedure 33
4.1 Experirnental setup ................................................................................ -33
4.2 Experimental procedure. ........................................................................ -35
4.3 Analysis of products. ............................................................................. -38
4.4 Mass balance and product distribution. .................................................. -39
4.5 Definitions of performance parameters used to compare catalytic
. .
actiwty. ................................................................................................. -40
ResuIts and Discussion 41
5.1 Catalyst screening. ................................................................................ -41
5.2 Cornparison with results fiom literature. ............................................... -42
5.3 Effect of metd loading ......................................................................... -44
. .
5.4 Effect of catalyst composition. ............................................................. -48
5.5 Effect of pressure ................................................................................. -49
5.6 Effect of temperature ............................................................................ 52
. .
5.7 Effect of feed composition. .................................................................. -61
Stability tests ....................................................................................... -70
Summary and Conclusions
Bibliography
Appendices 86
Al Liquid chromatograph spectm for a typical sarnple ............................. 86
A2 Calibration curves for liquid chromatograph. ........................................ -87
List of Tables
3.1 Various supports used in this study ..................................................................... 26
3.2 Characteristics of Pd/SDB catalysts. .................................................................. 29
3.3 Characteristics of Pd-PtISDB,P d-ir/SDB/P d-Ru/SDB catalysts. ......... ... .... ..30
5.1 Effect of various supports on the activity of the catalyst ............................ ... ..... ..43
5.2 Cornparison with redts fiom literature .............................................................. 43
5.3 ResuIts of catalytic behavior with dierent active componerits ............................ 48
5.4 Values of rate constants and rate orders with the. ................. ............ . ........... 70
List of Figures
2.1 Acrylate manufacturing technologies ................................................................. -7
2.2 Two stage propylene oxidation process ........................................................... -12
2.3 Chemistry of the liquid phase oxidation process ............................................... -21
4.1 Schematic diagram of the flow reactor system .................................................. 36
Effect of metal loading on catalyst activity (slurry reactor). .............................. 45
EfEect of metai loading on catalyst activity (trickle bed reactor) ........................ 45
Dependence of yield on metal surface area ....................................................... 46
Effect of pressure ........................................................................................... -50
Propylene conversion vs . time at different temperatures. ................................. -53
Effect of temperature on catalyst activity ........................................................ -54
Arrhenius type plot at 60 minutes ................................................................... -57
Possible kinetic regimes in a gas-phase reaction occurring
on a porous solid catalyst (C.N. Satterfield, 1980). .......................................... 58
Propylene conversions vs . thea t varying feed compositions ........................... 62
Oxygen conversions vs . tirne at varying feed compositions ............................. -63
Carbon dioxide selectivity vs . the at varying feed compositions .................... -64
Rate of propylene conversion vs . time for varying feed compositions .............. 66
Rate of propylene conversion vs . feed composition ........................................ -67
Rate constant vs . time .................................................................................... -70
Aging tests (C3c onversions vs . time) ............................................................. -72
Decrease of acryiic acid yield with each successive run .................................... 72
IR spectroscopic spectra for fresh and used catalyst ......................................... 77
5.18 X-Ray dfiactiion patterns for fresh and used catalyst.. ... .... .. ... .. . . . .... .. ...... .. - 78