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High Octane Ethers From Synthesis Gas-Derived Alcohols. Final Technical Report. September 25, 1990-December 24, 1993 - 1994

Klier, Kamil
Herman, Richard G.

Zettlemoyer Center of Surface Studies
Lehigh University

Table of Contents 633pdf

Section 1
961kb		 Title Page 1
Disclaimer 2
Executive Summary 3
Table of Contents 5
List of Figures 7
List of Tables 12

I

 Background C5 Ether Synthesis 14
 

A

 Selection of the Organic Resin Catalysts 16

B

 Experimental Testing of the Catalysts 17
II. MTBE Synthesis From Methanol and Isobutene Over Resin Catalysts 20
 

A

 Comparison of Acidic Ion-Exchange Resin Catalysts 20

B

 Temperature Dependence of MTBE Synthesis Over Purolite 22

C

 Space Velocity Dependence Over Purolite 23
III Ether Synthesis From Methanol and Isobutanol Over Resin Catalysts 25
 

A

 Ether Synthesis Via Coupling of Methanol and Isobutanol 25

B

 High Temperature Testing of Nafion-H MS, and Nafion-K 30

C

 Nafion-H MS Activity Dependence on Sodium Content 31
Section 2
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D

 Characterization of Newer Amberlyst Catalysts 33

E

 Mechanism of MIBE Formation Over Nafion-H:  Isotope Labelling Study of Ether Synthesis Over Nafion-H 51
Section 3
730kb		 IV Inorganic Catalysts for Direct Coupling of Alcohols to Ethers 58
 

A

 Standard Test Screening of Inorganic-Based Catalysts 58

B

 Effect of Water on the Reaction Rate Over y-Alumina 68
Section 4
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C

 Dehydration of Alcohols Over Silica and Zirconia Supported PW12 Heteropolyacid, Nb2O5, and Fe/Mn/ZrO2/SO42 Catalysts 72

D

 Dehydration of Isobutanol Over H-Mordenite 89

E

 X-Ray Powder Diffraction of H-Mordenite and H-ZSM-5 Zeolites 90
Section 5
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F

 Scanning Electron Microscopy of H-Mordenite and H-ZSM-5 Zeolite 95

G

 Molecular Modelling of Alcohol Reactions in H-Mordenite 101
V Extended Reactivity Studies Over the ZrO2/SO42- Catalyst 107
 

A

 Alcohol Pressure Dependence on Product Selectivity 107

B

 Reaction of Methanol/Isobutanol Mixture over ZrO2/SO42- 110

C

 Effect of Isobutanol Pressure on Mixed Alcohol Dehydration 115

D

 Pressure Dependence of Isobutanol Dehydration 115
Section 6
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E

 Pressure Dependence of Isobutanol Dehydration 117

F

 Dehydration of Isobutanol Only Over ZrO2/SO42- 117

G

 Dehydration of Primary Alcohols Over the ZrO2/SO42- Catalyst 124

H

 The Effect of Water on Reaction of MeOH/i-BuOH over ZrO2/SO42- 124
VI Characterization of the ZrO2/SO42- Catalyst 129

A

 Surface Area of the ZrO2/SO42- Catalyst 129

B

 Calculation of Amount of Sulfur on Sulfated Zirconia 131

C

 Determination of Activity via Aqueous Titration of ZrO2/SO42- 133

D

 Catalyst Characterization using Z-Ray Photoelectron Spectroscopy (XPS) 137
Section 7
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E

 Probing the Activity of Sulfate-Modified Zirconia by XPS 141

F

 Quantification of XPS Data: Amount of Sulfur on Sulfate-Modified Zirconia 146
VII Octane and Cetane Number Determination 149
 

A

 Octane Number Determination 149

B

 Cetane Number Determination 150
VIII Experimental Methods 151
 

A

 Calibration of Thermal Response Factors and GC Parameters 151

B

 Gas Chromatographic Analysis with Mass Spectrometric Detection 153
Section 8
654kb

C

 1H NMR to Resolve Whether 1-Butene was a Product 154

D

 Liquid Phase Alcohol Coupling Reactions 155
IX Conclusions 160
X Acknowledgements 163
XI References 164