Section 1
483kb

1.0

Contract Objective

2.0

Organization

3.0

Executive Summary

3.1

Goals and Approaches

3.2

Task 1 - Modifications of Ruthenium Catalysts

3.3

Task 2 - Development of Novel Catalysts

3.4

Task 3 - Further Study of Superior Catalysts

3.5

Conclusions

4.0

Experimental Data

4.1

Task 1:  Modifications of Ruthenium Catalysts

4.1.1

Ruthenium Catalysts for Direct Syngas Conversion

4.1.1.1

Introductions

Section 2
284kb

4.1.1.2

Effect of Iodide Concentration

4.1.1.3

Effect of Acidity on Ruthenium Catalyst Systems

4.1.1.4

Effect of Solvent Polarity on Ru/I/La Catalyst

4.1.1.5

Added Methanol Hydroformylation Catalysts

4.1.1.6

Product Distribution vs. H₂/CO Conversion

Section 3
261kb

4.1.1.7

Comparison of Additives LaCl₃ and SmCl₃

4.1.1.8

Comparison of Additives SmI₃ and SmCl₃

4.1.1.9

Use of Ruthenium Cyclopentadienyl Complexes

4.1.1.10

Effect of Added Water

4.1.1.11

Effects of Solvents on Ruthenium Catalysts

4.1.1.12

Effects of Lewis Acids on Ruthenium Catalysts

4.1.1.13

Lanthanide Promoters in Phosphonium Salt Solvent

Section 4
277kb

4.1.1.14

Effects of Metal-Containing Additives

Section 5
334kb

4.1.1.15

Effects of Organic Additives

4.1.2

Ruthenium Catalysts for Methanol Homologation

4.1.2.1

Introduction

4.1.2.2

Effects of Catalyst Additives on Homologation

4.1.2.3

Screening of Other Catalysts for Homologation

4.1.2.4

Studies of Catalyst Composition

Section 6
472kb

4.1.2.5

The Effect of Temperature on Homologation

4.1.3

Task 1 Summary

4.2

Task 2 - Development of Novel Catalysts

4.2.1

Cobalt Catalysts

4.2.1.1

Introduction

4.2.1.2

Novel Solvents with Cobalt Catalysts

Section 7
391kb

4.2.1.3

Methanol Homologation with Cobalt Catalysts

4.2.1.4

Reactions of Novel Cobalt Catalysts

4.2.2

Copper Catalysts

4.2.2.1

Introduction

4.2.2.2

Effect of Solvent in the Cu/Methoxide System

4.2.2.3

Effect of the Type of Base in the Cu System

4.2.2.4

Effect of Additives on the Cu/Methoxide System

4.2.2.5

Esters as Substrates in the Cu/Methoxide System

4.2.2.6

Copper Catalyst Recycle Experiments

4.2.2.7

Amine Trapping Agents in the Copper System

Section 8
442kb

4.2.2.8

Reactivity of a Cu Cyclopentadienyl Complex

4.2.2.9

The Copper System Under Standard Conditions

4.2.2.10

Identification of Solids Formed

4.2.2.11

New Solvents for the Copper System

4.2.2.12

New Ligands for the Copper System

4.2.2.13

Investigation of Cupric Methoxide

4.2.2.14

Redox Control in the Copper System

4.2.2.15

Investigation of Other Bases

4.2.2.16

Attempts to Increase Hydrogenation Activity

4.2.2.17

Copper Hydride in the Copper/Methoxide System

Section 9
307kb

4.2.2.18

The Copper/Methoxide System in Dry Solvents

4.2.2.19

Investigation of a Complex Reducing Agent

4.2.3

Iron Catalysts

4.2.3.1

Introduction

4.2.3.2

Reduction of CO by Everitt's Salt System

4.2.3.3

Everitt's Salt System Under Pressure

4.2.4

Other Catalysts

4.2.4.1

Introduction

4.2.4.2

Novel Solvent-Metal Combinations

4.2.4.3

Effects of Solvents on Rhodium Catalysts

4.2.4.4

Low Pressure Runs with Cu and Co Complexes

4.2.4.5

Screening of Various Other Catalysts

Section 10
396kb

4.2.5

Task 2 Summary

4.3

Task 3 - Further Study of Superior Catalysts

4.3.1

Ruthenium-Based Catalysts for Methanol Homologation

4.3.1.1

Introduction

4.3.1.2

Scale-up of the Methanol Homologation System

4.3.1.3

Statistically Designed Experiments

Section 11
347kb

4.3.1.4

Studies of Catalysts Composition and Precursors

4.3.1.5

Studies of Catalysts Additives and Solvents

Section 12
636kb

4.3.1.6

Further Studies of Catalyst Additives

4.3.2

Task 3 Summary

5.0

Conclusions and Opportunities for Future Research

6.0

Appendixes

6.1

Appendix A.  Use of Code System

6.2

Appendix B.  Procedures for Catalyst Testing

6.3

Appendix C.  Procedures for Product Analysis