General Disclaimer One or more of the Following Statements may affect this Document This document has been reproduced from the best copy furnished by the organizational source. It is being released in the interest of making available as much information as possible. This document may contain data, which exceeds the sheet parameters. It was furnished in this condition by the organizational source and is the best copy available. This document may contain tone-on-tone or color graphs, charts and/or pictures, which have been reproduced in black and white. This document is paginated as submitted by the original source. Portions of this document are not fully legible due to the historical nature of some of the material. However, it is the best reproduction available from the original submission. Produced by the NASA Center for Aerospace Information (CASI) NASA CR - 159480 EXXON/GRUS. 1KWD. 78 NIGH PERFORMANCE, HIGH DENSITY HYDROCARBON FUELS J. W. Frankenfeld, T. W. Hastings, M. Lieberman and W. F. Taylor EXXON RESEARCH AND ENGINEERING COMPANY prepared for NATIONAL AERONAUTICS AND SPACE ADMINISTRATION (NASA-CR-159''PO) HIGH PEPPOFMANCF, HIGH V79-20267 DENSTTv HYDR I-CARBON FTIELS (Exxon P.esearch and Engineering Co.) 239 rp HC A11/MF A01 CSCL 21D 'Inclas G3/28 19456 NASA Lewis Research Center Contract NAS 3-20394 Qnr{l,,Y^ ^'Pr I€ ^i NASA CR - 159480 EXXON/GRUS . 1KWD . 78 L: HIGH PERFORMANCE, HIGH DENSITY HYDROCARBON FUELS J. W. Frankenfeld, T. W. Hastings, M. Lieberman and W. F. Taylor EXXON RESEARCH AND ENGINEERING COMPANY prepared for NATIONAL AERONAUTICS AND SPACE ADMINISTRATION NASA Lewis Research Center Contract NAS 3-20394 FOREWARD The research described in this report was performed at Exxon Research and Engineering Company, Linden, New Jersey and Contract NAS 320394 with Mr. J. J. Notardonato, NASA-Lewis Research Center as Project Manager. The period of performance for the technical portion of the program was 12 April 1977 to 12 June 1978. The authors wish to acknowledge the efforts of Mr. Robert Bruncati and Mr. Joseph Rehberger for their technical assistance. r S 'Y ..r L TABLE OF CONTENTS SECTION PAGE I SUMMARY I,1 Purpose and Scope . • . 1 1.2 Method of Approach . • . • • 1 1.3 Results . 1 1.3.1 High Impulse, Low Density Hydrocarbon Fuels • + , , . 2 1.4 Conclusions and Recommendations • , , , , , , • • . , , 2 II INTRODUCTION • , • . 4 I1.1 Background and Objectives , . • . + . 4 II.2 General Method of Approach • • O , , , . , , , , • + • 5 .9 , II.3 Task Statement and Description , . , , . , + + . 5 II.3.1 Task (1) Fuel Candidate Screening and Selection 5 II.3.2 Task (2) Fuel Physical Property Evaluation 7 II.3.3 Task (3) Fuel Production Economics . • . , . 8 II.3.4 Task (4) Advanced Hydrocarbon Fuel Analysis 8 11.3.5 Task (5) Reports . 8 III RESULTS AND DISCUSSION . 9 III.1 Task 1 Fuel Candidate Screening and Selection . • . 9 III.1.1 Method of Approach - Selection Guidelines • . .. 9 III,1.2 Pure Compound Candidates . • . • . 11 III.1.3 Chemical Plant Streams . 12 111.1.3.1 Modified Chemical Plant Streams . 12 III.1.4 Candidate Refinery Streams . 16 111.1.5 Ranking of Candidates by Estimated Critical . 18 Properties Y _. 1 SECTION PAGE III,1.6 Ten Candidates for Continued Research . 20 III.2 Task (2) Fuel Physical Property Evaluation . 22 III.2.1 Elemental Analysis of Top Candidates. , . 22 1II.2.2 Heats of Combustion - ASTM D238t. 22 I11.2.2.1 Heats of Formation from Measured Heats 24 of Combustion . 111.2.2.2 Rankings by and Merit Index (p I sp3 ) 24 Using Measured Values . , . 1II.2.3 Densities as a Function of Temperature . , . 28 III.2.4 Freezing Points . 28 111.2.5 Viscosities as a Function of Temperature . , 28 111.2.5.1 Improving Viscosity by Blending 28 1I1.2.6 Vapor Pressure Measurements . , . 33 1II.2.7 Thermal Stability Measurements. 33 III.2.8 Gas Chromatographic Distillations . 34 111.2.9 Thermal Conductivities of Candidate Fuels 34 111.3 Task (3) Fuel Production Economics. 38 III.3.1 Costs of Chemical Plant and Refinery Streams 38 III.3.2 Costs of Modified Chemical Plant Streams 38 and Pure Compounds III.3.Z.1 Production of B-20 (Modified Chem Plant . 38 Stream B-11) 111.3.2,2 Production Costs for Cyclo- dodecatriene (A-5) and 41 Decahydroacenaphthene (A4) SECTION PAGE III.4 Task (4) Advanced Hydrocarbon Fuel Analysis. , . 45 II1.4.1 Synthesis of Highly Energetic Hydrocarbons , . 45 111.4.1.1 Modification of Existing High Energy 46 Candidiate Fuels I11.4.1.2 Synthesis of New Types of Molecules , . 46 III.4.2 Liquid Derivatives from Shale and Coal , , , , , , . 48 111.4.2.1 Liquid Fuels from Oil Shale , , , , , , , 48 I11.4.2.2 Liquids from Coal , , , , , , . , , , . 48 III.4.3 Analysis of Fuel Slurries as Energy Dense Fuels, . , 51 111.4.3.1 Use of Light Metal Slurries . , , . 51 111.4.3.2 Carbon Slurry Fuels , . , . 52 II1.4.4 Analysis of Additives or Modifications to Improve, . 53 Viscosity and Thermal Stability 111.4.4.1 Viscosity Modifications , . , , , , , , , 53 I11.4.4.2 Thermal Stability Modifications . , , , . 55 111.5 High Impulse, Low Density Fuel Candidates . , , , . , . 56 IV CONCLUSIONS AND RECOMMENDATIONS . 61 IV.1 Conclusions . 61 IV.2 Recommendations for Additional Research. , . , , , . 62 V REFERENCE . 65 APPENDIX A Estimated Physical Properties of Candidate . , 67 Fuels and Methods of Estimation A-1 Introduction . 68 A-2 Estimates of Heat of Formation and, . , . 70 Combustion for Pure Liquid Compounds A-3 Estimating Properties for Mixed Compound 93 Streams of Unknown Composition A-4 Effects of Hydrogentaion and . 97 Distillation on Estimated Stream Properties SECTION PACE A-5 Specific Impulse and Merit Index . 98 Estimations of Streams A-6 References to Appendix A . 106 APPENDIX B Methods of Analysis and Tables for Data • . • • • • 101 Extrapolation B-1 Reid Vapor Pressure Charts for Pure 108 Compounds and Chem Plant Streams B-2 Reid Vapor Pressure Charts for . • • . 109 Refinery Streams B-3 Details of the Exxon Advanced Fuel • . 112 Unit B-4 System for the 6ravimetric Measurement • • . 118 of Carbonaceous Deposits APPENDIX C Compositions and Estimated Critical Properties 122 of Candidate Fuels C-1 Composition of Chemical Plant Streams • . • . 123 C-2 Composition and Estimated Properties of • • . 124 Chemical Plant Blends C-3 Inspections and Compositional Data on • • • . 126 Refinery Streams APPENDIX D Ranking of Fuel Candidates . 144 D-1 Parameters for Ranking. 145 D-2 Ranking by Merit . Index (p I sp 3 ). • . 149 D-3 Ranking by p I sp . 150 D-4 Ranking by Specific Impulse (I sp ) . 152 D-5 Ranking by Estimated Volumetric Heat . 155 of Combustion 4 SECTION PAGE APPENDIX E Tables and Plots of Some Physical Properties . 158 for Top Fuel Candidates E-1 Effects of Temperature on Density for . 159 Pure Compounds E-2 Effects of Temperature on Density for . .. 160 Chemical Plant Streams E-3 Effects of Temperature on Density for . 161 Refinery Streams E-4 Semilog Plots of Viscosity vs. Temperature 162 for Pure Compounds E-5 Semilog Plots of Viscosity vs. Temperature 163 for Chemical Plant Streams E-6 Semilog Plots of Viscosity vs. Temperature . 164 for Refiner y Streams E-7 Semilog Plots of Viscosity vs. Temperature 165 for Stream Blends E-8 Semilog Plots of Viscosity vs. Temperature . 166 for Stream Blends E-9 Thermal Stability - Arrhenius Plots for . 167 Some Pure Compound Candidates E-10 Arrhenius Plots for Some Chemical Plant . 168 Streams E-11 Arrhenius Plots for Refinery Streams . 169 E-12 G. C. Distillation Curves for Chemical Plant 170 Streams E-13 G. C. Distillation Curves for Chemical Plant 171 Streams E-14 G. C. Distillation Cuves for Refinery Streams. 172 APPENDIX F Synthesis of Pure Compound Candidates and Modified 173 Chemical Plant Streams F-E Synthesis of Decahydroacenaphthene (A-6) . 173 F-2 Conversion of F-4 to B-20 , , _ , , , , , , , , 173 SECTION RAGE APPENDIX G Advanced Hydrocarbon Fuel Analysis. 175 G-1 Synthesis of New, Energy Dense . , 176 Compounds G-2 !.(quids from Shale and Coal as . 195 Sources for Energy Dense Fuels G-3 Carbon Slurry Fuels . 207 G-4 Additives and Modification for . , . 210 Improving Viscosity and Thermal Stability a LIST OF TABLES TABLE PAGE 1. Effects of Structure on Critical Properties 13 2. Most Promising Pure Compound Candidates 14 3. Chemical Plant Streams as Candidates for High 15 Density Fuel 4. Modified Chemical Plant Streams - Effects of 17 Hydrogenation and Distillation 5. Refinery Streams as Candidates for High Density 19 Fuels 6. Ten Candidates Seler-+_J for Further Research 21 7. Elemental Analysis for Top Fuel Candidates 23 8. Heats of Combustion for Candidate Fuels 25 9. Heats of Formation of Top Candidates from Measured 26 Heats of Combustion 10. Merit Indices and I Values for Top Candidates 27 Based on Measured 09lues 11. Densities of Top Candidates as A Function of 29 Temperature 12. Freezing Points of Top Fuel Candidates 30 13. Viscosities of Top Candidates as Function of Temperature 31 14. Viscosities of Some Candidate Blends as a Function of 32 Temperature 15. Vapor Pressure Measurements of Top Candidates 35 16. Thermal Stability of Top Fuel Candidates 36 17. Thermal Conductivities of Candidate Fuels 37 18. Costs for Chemical Plant and Refinery Stream Candidates 39 19. Projected Production Costs for Pure Compounds and a 14 Modified Chemical Plant Stream 20. Comparison of Key Properties of High Performance 17 r _ Liquid Fuels TABLE PAGE 21. Analysis of Kerosene Fractions of Hydrotreated Paraho 49 Shale Liquid 22. Energy Properties of Shale Liquids Compared to Other 50 Candidiate Fuels 23. Advantages of Carbon Slurry Fuels 52 24. Effects of CarbonSlurra in;l on Some Energy Properties 54 of RP-1 25.