Hydrogen sulfide amine conversion

The work of Nazarov on vinyl ethynyl carbinols involves condensation of vinylacetylene with ketones in the presence of caustic potash and also their conversions, many of which are catalytic in nature. A review of his work involving polymerization, isomerization, hydrogenation, and other conversions was published by him (252). Hydration of divinylacetylenes in methanol solution in the presence of mercuric sulfate and sulfuric acid gave vinyl alkyl ketones. These can be reacted with hydrogen sulfide, amines, etc., to yield heterocyclic compounds. Substituted vinyl alkyl ketones underwent spontaneous cyclization to cyclopentenones. Nazarov summarized a decade of this research in this field in 1951 (253). His general review of organic syntheses based on acetylene is also of interest in this connection (254). 

The reactions in Methods A, B and C, which all start from pyrylium salts are analogous to the well-known conversions of 2.4.6-substituted pyrylium salts 27 with ammonia, primary amines, hydrogen sulfide or the anions of CH activated compounds to the corresponding heterocyclic or isocyclic aromatic systems The first step involves addition of the basic phosphine at C-2 (or C-6) to form 2S. Ring-opening, ring-closure and elimination of water are likely steps in the formation of the product 2. 

Furans can be converted into N- alkylpyrroles by heating with primary amines and alumina. Similar thermal conversions of furans and benzo[6]furans to their sulfur analogues in the presence of alumina or other metal oxide catalysts and hydrogen sulfide are also known. l,3-Diphenylbenzo[c]furan is converted into the thiophene by heating with phosphorus pentasulfide. The mechanism of these reactions is obscure. 

The thermoset polymers are usually obtained in quantitative yields. They are tough and can be molded into clear, tough films. Reaction of the polycarbodiimides with mono amines gives rise to the formation of polyguanidines. Also, conversion into polyureas with water, polythioureas with hydrogen sulfide and poly(O-alkylisoureas) with alcohols is known. ... 

The high concentration of hydrogen sulfide obtained by heating the amine salt may then be easily and economically converted to elemental sulfur via the Claus process. The Stretford process, which may also be used for hydrogen sulfide capture, accomplishes both capture and conversion using an aqueous mixture of 1,5-, and 1,8-disulfonic acids of 9,10-anthraquinone (AQ) to sulfur in a single step [38] (Eq. 3.21). 

When the nucleophile has hydrogen atoms, e.g., with ammonia, primary amines, hydroxylamine, hydrazine derivatives, phosphine, hydrogen sulfide, nitromethane (EWG = NO2), acetonitrile (EWG = CN), an ANRORC (attack by nucleophile, ring opening, ring closure) reaction results in the conversion of substituted pyrylium salts into a large variety of six-membered aromatic carbocyclic or heterocyclic compounds. 

Hydrogen Sulfide Removal. When sulfiir-containing feeds pass through hydrotreaters or conversion units, some or most of the sulfur is converted into H2S, which eventually ends up in off-gas streams. Amine absorbers remove the H2S, leaving only 10 to 20 wppm in the treated gas streams. H2S is steam-stripped from the amines, which are returned to the absorbers. The H2S goes to the refinery sulfur plant. 

Several processes have been developed based on the oxidation approach, but, with some exceptions, such as the Linde Clintox process (Heisel and Marold, 1992) these have not been commercial successes because of the complexity of SO2 recovery processes and their comparatively low SO2 removal efficiencies. Hydrogen sulfide, on the other hand, can be removed at very high efficiency by a number of processes, including the selective amine processes discussed in Chapter 2. Processes that involve the conversion of Claus plant tail gas sulfur compounds to H2S and the removal of this H2S are discussed in the following sections. Processes reviewed include Parson s Beavon Sulfur Removal (BSR) process. Shell s SCOT process, FB and D Technologies Sulften process, the TPA Resulf process, and the Exxon Flexsorb SE Plus process. 

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