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The Action of Tetramethylurea and Hexamethylphosphoramide

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The Action of Tetramethylurea and Hexamethylphosphoramide The action of tetramethylurea and hexamethylphosphoramide blended with other solvents on the dissolution of coal by Timothy Lee Ward A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemical Engineering Montana State University © Copyright by Timothy Lee Ward (1984) Abstract: Tetramethylurea (TMU) and hexamethylphosphoramide (HMPA) were blended with a number of other solvents to determine the solvent action and effectiveness of the blends on extraction of coal as compared with that of unblended TMU/HMPA (TMU and HMPA In a 50/50 mixture). Dissolution to more than 41% was observed using 33% tetralin blended with 67% TMU/HMPA on Kittaning coal at 320°F, compared to a maximum of 40.7% dissolution observed with unblended TMU/HMPA. It was found that aromatic/hydroaromatic solvents such as tetralin, napthalene, and l-me-napthaIene, which are relatively inert toward coal at temperatures below 350°F, could be blended up to 80% by volume with TMU/HMPA without significantly reducing the ultimate dissolving power below that of unblended TMU/HMPA. Use of 80% decalin and 80% limonene blended with TMU/HMPA resulted in substantially lower extraction than unblended TMU/HMPA. Isopropyl alcohol, when blended with TMU/HMPA in amounts greater than 10%, was found to result in a substantial decrease in dissolving ability. The apparent dissolution rate for a blend of 80% tetralin and 20% TMU/HMPA is lower than for unblended TMU/HMPA, however the ultimate dissolution attained is approximately equal. At 320°F much of the ultimately attainable dissolution with TMU/HMPA and 80% tetralin blended with TMU/HMPA occurs within 5 minutes, with slow or even retrogressive dissolution after that. Solubility parameters were considered and found to be helpful in correlating dissolution effectiveness of solvent blends tested. TMU and HMPA are retained in the extraction residue in the amount of, typically, 5-15% by weight and tetralin retention of 8-10% was indicated for a pure tetralin extraction at 320°F. Relation of solvent retention to extraction variables was discussed. THE ACTION OF TETRAMETHYLUREA AND HEXAMETHYL PHOSPHORAMIDE BLENDED WITH OTHER SOLVENTS , ON THE DISSOLUTION OF COAL by Timothy Lee Ward A thesis submitted in partial fulfillment. of the requirements for the degree of Master of Science in Chemical Engineering ' » I'--!-,- V I , MONTANA STATE UNIVERSITY Bozeman( Montana February 1984 Main lib waiipN 3 7 % ii dop.S' APPROVAL of a thesis submitted by Timothy Lee Ward This thesis has been read by each member of the thesis committee and has been found to be satisfactory regarding content, English usage, citations, bibliographic style, and consistency, and is ready for submission to the College of Graduate Studies. Jj/ /6 7 Date rperson, Graduate Committee Approved for the Major Department Date Hi Major Department Approved for the College of Graduate Studies Date Graduate Dean iii STATEMENT OF PERMISSION TO USE In presenting this thesis in partial fulfillment of the requirements for a master's degree at Montana State University„ I agree that the Library shall make it avail­ able to borrowers under rules of the Library. Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgement of source is made. Permission for extensive quotation from or reproduct ion of thesis may be granted by my major professor, or in his absence, by the Director of Libraries when, in the opinion of either, the proposed use of the material is for scholarly purposes. Any copying or use of the material in this thesis for financial gain shall not be allowed without my written permission. Signature Date iv ACKNOMJ MT The author expresses his appreciation to thd faculty and staff of the Chemical Engineering Department at Montana State University for their help and guidance. Special thanks is extended to Dr. John Sears for his support and help throughout the conduct of the research and preparation of this thesis. Special thanks is also extended to Dr. Doug, Smith and to my coworkers, I Hsing Tsao and Christina Ichioka. V TABLE OF CONTENTS Page 1. LIST OF TABLES.... ............... vii 2. LIST OF FIGURES... ..... viii 3. ABSTRACT........ ix 4. INTRODUCTION............. I TMU and HMPA.. Solvent Theory M CO Related Work on Solvent Extraction of Coal... 11 Research Objective............ 16 5. EXPERIMENTAL..................... 18 Materials................................... 18 Experimental Procedure......... 21 Analytical Procedures................. 25 Error and Reproducibility................... 27 6. RESULTS AND DISCUSSION.... ............... 33 TMU/HMPA/Tetralin Blends.................... 33 Dissolution Rate in Tetralin Blends.... .... 34 Effect of Amount of Tetralin in Blends...... 40 Other Solvent Blends..................... 43 Correlation of Solvent Blend Behavior....... 44 Solvent Retention........................... 56 7. SUMMARY... ............ 67 8. RECOMMENDATIONS FOR FUTURE RESEARCH...... 69 9. NOMENCLATURE.................................. 71 10. REFERENCES CITED................. 73 vi TABLE OF CONTENTS— Continued Page APPENDICES............ ........................... 78 Appendix A-Raw Data from Extraction Experiments...................... 79 Appendix B-Raw Results from Extraction Experiments................. 87 Appendix C-Sample Calculations.......... 93 Appendix D-TMU Solubilities................. 99 Vii LIST OF TABLES Page 1. Physical Constants of TMU and HMPA............ 5 2. Solvent Groups According to Donor- Acceptor Model................. 15 3. Analyses of Coals Used......................... 19 4. Solvents Used................................. 20 5. Replicate Experiments to Observe Reproducibility............. 29 6. Potential Error Due to Assumption of Equal Nitrogen Percentage in Coal and Residue....... 31 7. Error Contributions to Total Estimated Error in Total Dissolution and Solvent Retention.... 32 8. Effect of Blending TMU„ HMPA and Tetralin......................... 34 9. Results Using Different Hydrocarbon Solvents Blended with TMU/HMPA......... 43 10. Solubility Parameters of Solvent Blends........ ............................ 47 11. Temperature Effect on TMU/HMPA Retention.... 59 12. Pyridine Extraction Results................... 62 13. Mass Balance Results for Pyridine Extractions......... 65 14. Raw Data from Extraction Experiments.......... 80 15. Raw Results from Extraction Experiments........ 88 16. Fortran Program for Calculation of Total Dissolution, Solvent Retention and Solvent Free Residue Properties.... 98 17. Solubilities of Various Substances in TMU at 22 0C ............ ....................... 100 viii LIST OF FIGURES Page 1. Structure of TMU and HMPA......... 4 2. Experimental Apparatus ..... 22 3. Dissolution vs. Time for TMU/HMPA and 80% Tetralin 20% TMU/HMPA Blend at Various Temperatures..... ............ ........ 36 4. Temperature Dependence of Average Dissolution Rate. ...... ...................... 38 5. Effect of Tetralin on Dissolution............. 41 6. Effect of Blending Isopropyl Alcohol with TMU/HMPA............. 45 7. Component Solubility Parameter Plot for Solvent Blends........................ 49 8. Component Solubility Parameter Plot for Various Solvents.......................... 51 9. Percent Dissolution vs. <SH for Solvent Blends at 320°F...... ......................... 53 10. Percent Dissolution vs. 6P for Solvent Blends at 320°F......... 53 11. Percent Dissolution vs. §D for Solvent Blends at 320QF. ....................... 54 12. Percent Dissolution vs. 6q for for Solvent Blends at 320°F........... ...... 54 13. Effect of Tetralin on TMU/HMPA Retention.............. 57 14. TMU/HMPA Retention vs. Apparent Dissolution.... 61 ix ABSTRACT Tetramethylurea (TMU) and hexamethylphosphoramlde (HMPA) were blended with a number of other solvents to determine the solvent action and effectiveness of the blends on extraction of coal as compared with that of unblended TMU/HMPA (TMU and HMPA In a 50/50 mixture). Dissolution to more than 41% was observed using 33% tetralin blended with 67% TMU/HMPA on Kittaning coal at 320qF, compared to a maximum of 40.7% dissolution observed with unblended TMU/HMPA. It was found that aromatic/hydroaromatic solvents such as tetralin, napthalene, and I-me-napthaIene, which are relatively inert toward coal at temperatures below 350°F, could be blended up to 80% by volume with TMU/HMPA without significantly reducing the ultimate dissolving power below that of unblended TMU/HMPA. Use of 80% decalin and 80% limonene blended with TMU/HMPA, resulted in substantially lower extraction than unblended TMU/HMPA. Isopropyl alcohol, when blended with TMU/HMPA in amounts greater than 10%, was found to result in a substantial decrease in dissolving ability. The apparent dissolution rate for a blend of 80% tetralin and 20% TMU/HMPA is lower than for unblended TMU/HMPA, however the ultimate dissolution attained is approximately equal. At 320°F much of the ultimately attainable dissolution with TMU/HMPA and 80% tetralin blended with TMU/HMPA occurs within 5 minutes, with slow or even retrogressive dissolution after that. Solubility parameters were considered and found to be helpful in correlating dissolution effectiveness of solvent blends tested. TMU and HMPA are retained in the extraction residue in the amount of, typically, 5-15% by weight and tetralin retention of 8-10% was indicated for a pure tetralin extraction at 320°F. Relation of solvent retention to extraction variables was discussed. I INTRODUCTION Since the
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