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species, it is anticipated that the more highly substituted and larger ring phenolics will be more difficult to hydrogenate by using this or a similar catalyst. Therefore their relative concentration will increase with further conversion.
Conclusions A study of the extraction and characterization of phenolics from coal-derived products from the Wilsonville facility was performed. Phenolics were separated from first-stage vapor condensates by aqueous sodium hydroxide extraction. For Illinois No. 6 coal with a thermal/catalytic mode, approximately 18 wt % of the liquid product was extracted with NaOH. For the Wyodak subbituminous coal, approximately 21 w t % of the liquid product was extracted. These phenolics consist of phenols, indanols, naphthols, and biphenylols/acenaphthols. Homologues containing one through four alkyl carbons predominate. Phenolics derived from both Illinois No. 6 and Wyodak coals have boiling points primarily in the range of 175-315
"C. The "ashy recycle" mode a t Wilsonville (namely, the recycle of some unconverted coal plus mineral matter with the solvent) exhibits a catalytic effect for increased deoxygenation over that occurring with recycle of only solvent plus residue. The use of Amocat-1A catalyst in the first-stage Wilsonville reactor results in further deoxygenation. This catalyst is somewhat specific in that it more easily reduces less hindered phenolics.
Acknowledgment. We are grateful to E. J. Bernier and T. L. Marker for their work on this project. We are also grateful to R. E. Lumpkin, B. A. Fleming, A. Basu, R. W. Dunlap, and E. G. Wollaston for their discussions, P. L. Baldwin for her extraction work, and W. H. Weber, J. M. Lee, and others a t the Wilsonville facility who helped in obtaining the samples and operating data. We also acknowledge the funding of the Wilsonville facility by the Department of Energy, The Electrical Research Institute, and Amoco Oil Company.
Coal Solubilization. Promotion of the C-Alkylation Reaction by n -Butyllithium and Potassium tert -Butoxide Kuntal Chatterjee,tp*Mikio Miyake,s and Leon M. Stock*>+ Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, a n d Department of Applied Chemistry, Osaka University, Osaka 565, J a p a n Received January 26, 1990. Revised Manuscript Received March 16, 1990
A new base-catalyzed C-alkylation reaction that employs a mixture of n-butyllithium and potassium tert-butoxide in refluxing heptane to produce coal anions that are subsequently treated with n-alkyl halides a t 0 OC has been developed and applied. Almost quantitative pyridine solubilization was achieved by C-octylation of a Lower Kittanning coal, PSOC 1197. C-Octylation was less successful for the solubilization of bituminous Illinois No. 6 coal, APCSP 3, and subbituminous Wyodak coal, APCSP 2, which gave 35 and 33% soluble material, respectively. Their 0-methyl derivatives yielded 43 and 20% soluble material in the same reaction. The observations are in accord with the concept of Ouchi and his associates that higher rank coals, although more aromatic in character, have a lower degree of polymerization than low-rank coals. In this situation relatively mild chemical reactions, such as C-alkylation, that lead to modest changes in molecular dimensions can disrupt intermolecular forces and accomplish solubilization of the high-rank coals.
Introduction Most chemical reactions that have been investigated for the transformation of coal to soluble products disrupt strong covalent linkages.'S2 More recently, interest has been directed to the application of simple alkylation reactions that can alter the nonbonded intermolecular interactions that contribute to the binding of large coal molecules in the solid state.2 These strategies are based on the idea that the introduction of an 0-alkyl group can eliminate hydrogen-bonding interactions and the introduction Of a group can disrupt polarization forces. Whereas, 0-alkylation does not generally enhance the solubility of either high- or low-rank to a significant C-alkylation is 'The University of Chicago. *Link Foundation Fellow, 1989-1990. Osaka University.
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effective for some high-rank coals?-1o Indeed, C-octylation with sodium amide in liquid ammonia converts a t least one low volatile bituminous coal from the Lower Kittanning (1) Davidson, R. M. Coal Sci. 1982, 1, 84. (2) Stock, L. M. Coal. Sci. 1982, 1, 161. (3) Mallya, N.; Stock, L. M. Fuel 1986, 65, 736. (4) Ignasiak, B.; Carson, D.; Gawlak, M. Fuel 1979, 58, 833. (5) Gawlak, M.; Carson, B.; Strausz, 0. P. Preprints of Papers, In-
ternational Conference on Coal Science, Maastricht, The Netherlands, 1987; P 57. (6) Lazarov, L.; Marinov, S. P.; Stefanova, M.; Angelova, G. Preprints of Papers, International Conference on Coal Science, Maastricht, The Netherlands. 1987: D 745. (7) Lazarov, L.;'Marinov, S. P. Fuel 1987, 66, 185. (8) Chambers, R. R.; Jr.; Hagaman, E. W.; Woody, M. C. Polynuclear Aromatic Hvdrocarbons: Ebert, L, Ed,: Advances in Chemistrv 217: American Chemical Society: Washington, DC, 1987; Chapter -15, p 255. (9) Miyake, M.; Stock, L. M. Energy Fuels 1988, 2, 815. (10) Chambers, R. R., Jr.; Hagaman, E. W.; Woody, M. C. Preprints of Papers, International Conference on Coal Science, Maastricht, The Netherlands, 1987; p 741.
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Coal Solubilization Seam, PSOC 1197, in which polarization forces are clearly more important than hydrogen-bonding forces, into a substance that is 90% soluble in ~ y r i d i n e . ~ The strengths of the bases that were used in the alkylation of this high-rank coal influenced the results significantly. There was a clear change in the solubility of the products that were obtained from the Lower Kittanning coal with sodium hexamethyldisilazide (pKa 26), sodium amide (pK, 35), and lithium diisopropylamide (pKa 36),g The weakest base, sodium hexamethyldisilazide, provided only 16% soluble material during butylation, whereas the stronger bases, sodium amide and lithium diisopropylamide, produced more than 50% soluble material in the same reaction? These observations suggested that other stronger bases might be even more effective reagents for solubilization and led us to consider the use of n-butyllithium (pK, 42) for C-alkylation. This reagent should be able to abstract protons from the weakly acidic aromatic carbon acids, pK, >35, as well as from the relatively strong benzylic carbon acids, pK, 0.6)OP rapidly decreases to lower values (110% approximately), making it difficult to infer, by the parameter alone, the different primary sources of organic matter. The oleanane threshold depth delimits the diagenesis/catagenesis boundary precisely and should correspond to the top of the oil-generative window (TOGW) in the area. The oleanane parameter can also be practically applied in distinguishing oils from different sources as well as oils formed from a common source, a t different thermal maturities, e.g., early versus late generated oils.
Introduction The search in the past few years for chemical fossils or molecular markers for reconstruction of palaeoenvironments has yielded useful indicators of Source input (provenance), palaeosalinity, palaeoecology, and thermal history.lV2 Present address: Gulf oil Company (Nigeria) Ltd., P.M.B. 2469, Lagos, Nigeria. * Author t o whom correspondence should be addressed.
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One of the most diagnostic classes of biomarkers of terrigenous input in oils and rocks is the oleanane group, which consists of pentacyclanes derived from amyrin, lupeal, and other related higher plant t r i t e r ~ e n o i d s . ~ - ~ (1)Mello, M. R.;Telnaes, N.; Gaglianone, P. C.; Chicarelli, M. I.; Brassel, S. C.; Maxwell, J. R. Org. Geochem. 1988,14, 31-45. (2) Mackenzie, A. S. In Adoances in Petroleum Geochemistry;Brooks, J., Welte, D., E&.; Academic Press: London, 1984;Vol. 1, pp 115-214. (3)Whitehead, E. V.In Advances in Organic Geochemistry; Tissot B., Bienner, F., Eds.; Technip: Paris, 1973;pp 225-243.
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