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Isobutanol-Methanol Mixtures from Synthesis Gas,
Final Technical Report

Iglesia, Enrique

University of California-Berkeley

In this pdf format, this document has 203 pages and is 1.95MB.

Table of Contents

1 CONTRACT OBJECTIVES AND TASKS
2 EXECUTIVE SUMMARY
3 EXPERIMENTAL, RESULTS, AND DISCUSSION
TASK 1: CATALYST SYNTHESIS 5
  1.1 METHANOL SYNTHESIS CATALYSTS 6
1.2 ALCOHOL COUPLING CATALYSTS 7
1.3 ISOBUTANOL AND METHANOL SYNTHESIS CATALYSTS 8
1.4 COPPER CATALYSTS SUPPORTED ON MODIFIED MgO 9
1.5 MODIFIED METHANOL SYNTHESIS CATALYSTS 14
TASK 2: CATALYST EVALUATION IN LABORATORY SCALE REACTORS 16
  2.1 BACKGROUND 16
2.2 ISOBUTANOL SYNTHESIS AT HIGH PRESSURE IN A CATALYTIC MICROREACTOR UNIT (CMRU) 18
  2.2.1 Effects of Catalyst Physical Properties on Activity - K - -CuxMgyCeOz 20
2.2.2 Effect of Alkali Identity on Cu/MgO/CeO2: K vs. Cs 22
2.2.3 Reproducibility of CMRU-unit 25
2.2.4 Methanol Synthesis 27
2.2.5 Bed Residence Time Effects 29
2.2.6 CO2-Addition Effects 31
2.2.7 Cu Concentration Effects 34
2.2.8 Effect of Replacing Ce with A1 in K-Cu0.5Mg5CeOx 36
2.2.9 Effect of substituting Ce with Zn in K-Cu0.5Mg5CeOx 38
2.2.10 Effect of adding small amounts of Pd 40
2.2.11 Effect of acid site tration after CuO Reduction 42
2.2.12 Effect of Cs Concentration 44
2.2.13 Alcohol Addition Studies 46
2.3 ISOTOPIC TRACER AND KINETIC STUDIES OF ALCOHOL COUPLING REACTIONS 52
  2.3.1 13CH3OH/C2H5OH Reactions on Cu/ZnO, Cs-Cu/ZnO and CuZnMnO Catalysts 53
2.3.2 Ethanol Reactions on Cu/ZnO, Mg5CeOx, and Cu0.5Mg5CeOx Catalysts 64
2.3.3 Ethanol Reactions on Copper Catalysts Supported on Modified MgO 67
2.3.4 Acetaldehyde Reactions on Isobutanol Synthesis Catalysts 81
2.3.5 C2H5OH/13C2H4O Reactions on Isobutanol Synthesis Catalysts 86
2.3.6 C2H5OH/D2 and C2H4O/D2 Reactions on Copper Catalysts supported on MgO 91
2.3.7 C2H4O/C2D4O reactions on copper catalysts supported on K-Mg5CeOx 101
2.3.8 Cross-Coupling Reactions of 13CH3OH/C2H4O and 13CH3OH/C3H6O 111
2.3.9 Methanol Reactions on Isobutanol Synthesis Catalysts and Their Individual Components 117
2.3.10 Cross-Coupling Reactions of 13CH3OH/C3H6O Mixtures on MgyAlOx 125
2.3.11 Ethanol Reactions on MgyAlOx 129
TASK 3: IDENTIFICATION OF REACTION INTERMEDIATED AND ACTIVE SITES 130
  3.1 TEMPERATURE-PROGRAM REDUCTION (TPR) OF MgO-BASED Cu CATALYSTS 130
3.2 DETERMINATION OF COPPER SURFACE AREA 133
3.3 DETERMINATION OF BASIC SITE DENSITY AND STRENGTH 136
3.4 TPSR OF ALCOHOLS AND ALDEHYDES ON ISOBUTANOL SYNTHESIS CATALYSTS 157
  3.4.1 Ethanol and Acetic Acid TPSR on Cs-Cu/ZnO/Al2O3 and ZrO2/MnO/ZnO 158
3.4.2 Ethanol TPSR Studies on Mg/Al Hydrotalcites 161
3.4.3 Acetaldehyde and Ethanol TPSR on CuMgCeOx Catalysts 163
3.5 IN-SITU IR STUDIES ON SURFACE INTERMEDIATE SPECIES DURING ETHANOL SURFACE REACTIONS 173
3.6 PROBING INITIAL C-C FORMATION FROM CO/H2 BY ISOTOPIC TRACER STUDIES IN CMRU-II 176
TASK 5: BENCH SCALE TESTING AT AIR PRODUCTS AND CHEMICALS 191
 
OTHER ACTIVITIES 193
ACKNOWLEDGEMENTS 196
REFERENCES 197