Action of Some Mercaptans in Hydrocarbon Solution on Copper and Copper Sulfide

Abstract

THE flotation process, organic sulfur compounds are selectively adsorbed by copper sulfide. Morgan and Sedbury (2) determined the heats of addition of some sulfur compounds with heavy metal salts, and found some of them to be large. It is well known that copper oxide was for a time used industrially in the removal of sulfur from petroleum fractions.These facts suggested a study of the removal of sulfur compounds from hydrocarbons by copper sulfide and similar materials. This investigation was started and carried through with the idea that only adsorption was involved. The results proved this to be wrong, but indicated instead unexpected reactions which are more important than the anticipated adsorption.

Self-Assembly of Photoluminescent Copper(I)−Dithiol Multilayer Thin Films and Bulk Materials

“…The Cu 2+ ion is known to react with thiols giving disulfides and Cu + . 11 Since the only thiol groups available for the reduction of Cu 2+ ions are confined to the surface of the Au substrate, the Cu(II) reduction step probably occurs with -SH oxidation and leads to the formation of surface bound disulfides, as illustrated in Figure 2. This assumption is supported by an experiment where the free thiol groups on the surface were diluted with n-pentanethiol to such an extent that disulfide formation becomes improbable (assuming no phase segregation of the two thiols).…”

“…Surprisingly, Cu was found to be already present in the +1 oxidation state with no evidence for the presence of Cu(II). The Cu 2+ ion is known to react with thiols giving disulfides and Cu + .…”

Effect of Sulfur and Sulfur Compounds in Naptha upon Certain Corrosion Tests

“…In the presence of air, copper powder reacts with mercaptans in hydrocarbon solution at 25°C. to give cuprous mercaptides and disulfides, but it is indifferent to alkyl sulfides and disulfides (10).…”

Metallic Salts of Alcohols and Alcohol Analogs.

“…Until the systematic study, as begun by Conant and McEwen (70), of the acidities of amines, alcohols, and mercaptans is farther advanced, judgment must be based on such occasional displacements as have been reported. Sodium sulfide is said to fail to neutralize a mercaptan, and even sodium hydrosulfide produces only a partial reaction (44), so that the ability of cupric sulfide to remove mercaptans from their solutions in hydrocarbons is unusual and unexplained (354). While the soluble alkali metal mercaptides are better prepared by the action of the free acids on metallic hydroxides or alkoxides, C2H6SH + NaOC2H6 -* NaSC2H6 + C2H5OH the extreme insolubility of the mercaptides and alkyl selenides of heavier metals makes it possible to precipitate them in the presence of hydrochloric acid.…”