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A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

Description: Remarkably mild conditions have been discovered for quantitative sulfur removal from dibenzothiophene and other organosulfur systems using relatively cheap elemental sodium. The project objectives are: (1) Optimize the coal desulfurization reaction with respect to time, temperature, coal type and the R groups (including R = H), and also on extraction, impregnation and sonication conditions; (2) Optimize the conditions for the HDS reaction (which allows the PR{sub 3} to function as an HDS catalyst for coal) with respect to R group, temperature, pressure, H{sub 2} gas flow rate and inert solvent presence; (3) Determine the product(s) and the pathway of the novel redox reaction that appears to quantitatively remove sulfur from dibenzothiophene (DBT) when R = Bu when FeCl{sub 3} is used as a catalyst; (4) Impregnate sulfur-laden coals with Fe{sup 3+} to ascertain if the PR{sub 3} desulfurization rate increases; (5) Determine the nature of the presently unextractable phosphorus compounds formed in solid coals by PR{sub 3}; (6) Explore the efficacy of PR{sub 3}/Fe{sup 3+} in removing sulfur from petroleum feedstocks, heavy ends (whether solid or liquid), coal tar and discarded tire rubber; (7) Explore the possibility of using water-soluble PR{sub 3} compounds and Fe{sup 3+} to remove sulfur from petroleum feedstocks and heavy ends in order to remove the SPR{sub 3} (and Fe{sup 3+} catalyst) by water extraction (for subsequent HDS of the SPR{sub 3}); and (8) Explore the possibility of using solid-supported PR{sub 3} compounds (plus Fe{sup 3+} catalyst) to remove sulfur from petroleum feedstocks and heavy ends in order to keep the oil and the SPR{sub 3} (formed in the reaction) in easily separable phases.
Date: August 31, 1997
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department

A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

Description: The nonionic superbase P(MeNCH{sub 2}CH{sub 2}){sub 3}N (A) efficiently desulfurizes trisulfides to disulfides and monosulfides, disulfides to monosulfides, and propylene sulfide to propene. S=P(MeNCH{sub 2}CH{sub 2}){sub 3}N (B) was formed as the sulfur acceptor. P(NMe{sub 2}){sub 3} was a much poorer desulfurizing agent than A under the same reaction conditions. Thiocyanates and triphenylphosphine sulfide were also desulfurized with A, but N-(phenylthio)phthalimide formed [A-SP]{sup +} phthalimide in quantitative yield.
Date: August 31, 1998
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department

A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

Description: The reactions of dialkyl mono- and disulfides and functionalized alkylthio compounds with sodium in refluxing hydrocarbon solvent (tetradecane, mesitylene or toluene) resulted in sulfur-free products in very high yields. Greater than 95% sulfur removal was observed when dialkyl mono or polysulfides were treated with Na in liquid ammonia. Polycyclic aromatic sulfur heterocycles were only moderately desulfurized under these conditions while phenylthio derivatives gave thiophenol as the major product and dithiophenols as the minor products.
Date: February 28, 1998
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department

A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

Description: A gas chromatographic method has been developed for the quantitation of sulfur removed from coal as tributyl phosphine sulfide (SPBu{sub 3}). This method also works very well for speciating and quantitating the products of sulfur removal from organosulfur removal from organosulfur compounds such as dibenzothiophene. Remarkably mild conditions have been discovered for quantitative sulfur removal from dibenzothiophene and other organosulfur systems using relatively cheap elemental sodium.
Date: October 1, 2000
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department

A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

Description: Column chromatographic separation of the S=PBu{sub 3}/PBu{sub 3} product mixture followed by weighing the S=PBu{sub 3}, and by vacuum distillation of S=PBu{sub 3}/PBu{sub 3}mixture followed by gas chromatographic analysis are described. Effects of coal mesh size, pre-treatment with methanol Coal (S) + excess PR{sub 3} {yields} Coal + S=PR{sub 3}/PBu{sub 3} and sonication on sulfur removal by PBu{sub 3} revealed that particle size was not observed to affect desulfurization efficiency in a consistent manner. Coal pretreatment with methanol to induce swelling or the addition of a filter aid such as Celite reduced desulfurization efficiency of the PBu{sub 3} and sonication was no more effective than heating. A rationale is put forth for the lack of efficacy of methanol pretreatment of the coal in desulfurization runs with PBu{sub 3}. Coal desulfurization with PBu{sub 3} was not improved in the presence of miniscule beads of molten lithium or sodium as a desulfurizing reagent for SPBu{sub 3} in a strategy aimed at regenerating PBu{sub 3} inside coal pores. Although desulfurization of coals did occur in sodium solutions in liquid ammonia, substantial loss of coal mass was also observed. Of particular concern is the mass balance in the above reaction, a problem which is described in some detail. In an effort to solve this difficulty, a specially designed apparatus is described which we believe can solve this problem reasonably effectively. Elemental sodium was found to remove sulfur quantitatively from a variety of polycyclic organosulfur compounds including dibenzothiophene and benzothiophene under relatively mild conditions (150 C) in a hydrocarbon solvent without requiring the addition of a hydrogen donor. Lithium facilitates the same reaction at a higher temperature (254 C). Mechanistic pathways are proposed for these transformations. Curiously, dibenzothiophene and its corresponding sulfone was virtually quantitatively desulfurized in sodium solutions in liquid ammonia at -33 C, ...
Date: November 1, 2001
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department