Formation of sulfur compounds in the hydrodenitrogenation of piperidine, pyridine, 1-pentylamine and 1-pent-4-enylamine on a nickel-tungsten catalyst in the presence of hydrogen sulfide

1982 ◽  
Vol 47 (3) ◽  
pp. 928-935 ◽  
Author(s):  
Mirko Černý

Hydrogenations of piperidine, pyridine, 1-pentylamine, and 1-pent-4-enylamine were carried out in an autoclave at 300°C on a sulfidized nickel-tungsten catalyst using either pure hydrogen or a mixture of hydrogen with hydrogen sulfide. Hydrogen sulfide was found to raise the degree of conversion of the starting substances and accelerate the hydrodenitrogenation by formation of sulfur compounds; 1-pentanethiol, di(1-pentyl)sulfide, 2-methylthiacyclopentane, thiacyclohexane and other sulfur compounds were detected in the reaction mixtures in the presence of hydrogensulfide. A reaction pathway is suggested of the hydrodenitrogenation of piperidine in the presence of hydrogen sulfide, accounting for the favourable effect of the latter on the hydrodenitrogenation of nitrogen compounds.

1983 ◽  
Vol 48 (12) ◽  
pp. 3413-3420 ◽  
Author(s):  
Mirko Černý ◽  
Antonín Trka

2-Methylquinoline, 2-methylpiperidine, indole, and isoquinoline were subjected to hydrodenitrogenation (HDN) on a sulphidized nickel-tungsten catalyst in an autoclave at 300 and 350 °C using pure hydrogen or a hydrogen-hydrogen sulphide mixture. The neutral fraction from the HDN of 2-methylquinoline and 2-methylpiperidine contained 40 and 90% sulphur compounds, respectively. The presence of hydrogen sulphide in the HDN of isoquinoline resulted in an enhanced fraction of the neutral moiety. A reaction mechanism is suggested for the HDN of 2-methylquinoline and 2-methylpiperidine in the presence of hydrogen sulphide, in which the latter contributes to the higher degree of conversion due to the formation of corresponding sulphur compounds.


1984 ◽  
Vol 49 (10) ◽  
pp. 2387-2392 ◽  
Author(s):  
Mirko Černý ◽  
Antonín Trka

Hydrodenitrogenations of aniline, cyclohexylamine, benzylamine, and 2-phenylethylamine were performed on a sulphided nickel-tungsten catalyst at 300°C in an autoclave filled with hydrogen in the absence and in the presence of hydrogen sulphide. Due to the presence of hydrogen sulphide the degree of conversion increased from 0.9 to 3,6% for aniline and from 72 to 99% for benzylamine, and the fraction of neutral substances increased from 2.4 to 7% for cyclohexylamine and from 5.0 to 8.9% for 2-phenylethylamine. The neutral fractions contained cyclohexanethiol, thiobenzamide, 2-phenylethanethiol, and other sulphur compounds giving evidence that the increased degree of conversion of the amines was due to the hydrogen sulphide taking direct part in the chemical reaction.


1971 ◽  
Vol 11 (03) ◽  
pp. 272-276 ◽  
Author(s):  
Jack G. Roof

Abstract The solubility of sulfur in hydrogen sulfide has been determined by an absolute method at 21 combinations of pressure and temperature within the range of 1,020 to 4,520 psia and 110 deg. to 230 deg. F. respectively. Results, which appear to be consistent within about 2 percent, show the solubility to increase with pressure along an isotherm but to pass through maxima along isobars. Where direct comparison can be made, our values differ drastically from published results at lower pressures and are in serious disagreement at higher pressures. The solubility of sulfur in carbon disulfide is reported for pressures from 1,020 to 5,020 psia at 150 deg. F. No published data were found for direct comparison. Both the solubility of sulfur and the density of saturated solutions decrease with increasing pressure at this temperature. Introduction Difficulties in production arise when a fluid containing a high content of hydrogen sulfide occurs in a reservoir in which elemental sulfur is present Changes in pressure and temperature present Changes in pressure and temperature can cause deposition of dissolved sulfur from hydrogen sulfide-rich fluids in both the formation and the production tubing. The first step in a study of this problem is to determine the solubility of sulfur in pure hydrogen sulfide under conditions of interest in production. This report presents results of one such study. Values published in the literature generally appear to be grossly in error. In some approaches to repairing the damage caused by sulfur plugging of formation and tubing, carbon disulfide is used as a solvent. Experiments were run at a typical temperature of 150 deg. F and elevated pressure to obtain basic data on the solubility of sulfur in carbon disulfide. SOLUBILITY OF SULFUR IN HYDROGEN SULFIDE EQUIPMENT AND MATERIALS Except for the items described, the equipment used in this study was of the type commonly found in a high-pressure laboratory. A schematic sketch of the equipment is show in Fig. 1. The equilibrium vessel was a thin-walled Teflon bag machined from solid bar stock to the shape indicated in Fig. 1. The bag, of a design suggested by R. H. Arntson, Shell Development Co., was approximately 2.25 in. OD and 5.9 in. long, with a wall thickness of 0.045 in. A split ring around the upper flange pulled the tapered neck of the bag snugly onto the projecting cone of the pressure vessel to seal against the mercury surrounding the bag. Two-way Valve B was used to shut off the pressure vessel from the crossline between Valves pressure vessel from the crossline between Valves A and C. Valve B was designed to have minimal dead volume below the Teflon washer packing. Sulfur was caught for weighing in a special glass trap, also shown in Fig. 1. This vessel was made of 35-mm OD pyrex Tubing and was about 7.5 in. in length. Each end terminated in precision-ground 0.25-in. tubing to accept Swagelok fittings. Each chamber included a coarse glass frit at its downstream end and was loosely filled with glass wool. Pressure was measured on a Heise gauge, which had been calibrated against an Aminco dead-weight gauge. Uncertainties in pressure should seldom exceed 5 psia. The pressure differential across the wall of the Teflon bag fell within this uncertainty in pressure. Temperature in the pressure vessel was measured by a tubular iron-constantan thermocouple inserted into a small hole in the bottom of the vessel. Emf of the couple was measured on a Rubicon potentiometer. The thermocouple had been calibrated potentiometer. The thermocouple had been calibrated against a platinum resistance thermometer. Uncertainties in temperature probably were not greater than 1 deg. F. A Thermotrol was used to control the temperature of the air thermostat. Both the precipitated sulfur and the carbon disulfide were Baker's Analyzed grade. SPEJ P. 272


2020 ◽  
Author(s):  
Nadezhda Titovna Berberova ◽  
Nadezhda Anatol’evna Pivovarova ◽  
Valentina Nikolaevna Storozhenko ◽  
Elena Vladimirovna Shinkar ◽  
Ivan Vladimorovich Smolyaninov

The tendency to reduce the content of sulfur compounds in particular H2S and low molecular thiols (RSH) in oil products sets the task of their extraction and disposal in order to obtain practically useful sulfur compounds. Hydrogen sulfide and thiols can be extracted from hydrocarbon fractions using N-methylpyrrolidone-as selective solvent. Hydrogen sulfide can be extracted from the residual oil products using a low energy exposure such as ultrasound and a constant magnetic field. The releasing gas is concentrated in N-methylpyrrolidone. Further, hydrogen sulfide and mercaptans can be used in the chemical synthesis of biologically active thioethers containing a catechol fragment. Another way of H2S and RSH utilization is the chemical adsorption of acidic components by modified polynuclear pivalate (acetate) zinc(II) silica gel. As a result of the interaction of complexes with H2S and RSH, it is possible to obtain zinc sulfide or zinc thiolates, which can be used in various fields of industry or agriculture. Hydrogen sulfide and thiols can also be applied in the electrochemical or microvaved assisted organic synthesis. This approach is promising from the standpoint of environmental safety of synthesis and low energy costs of the reactions. The SH-functionalization of hydrocarbons (indan, indene, decalin, tetralin, naphthalene and 1,2-dihydronaphthalene) leads to obtain biologically active compounds. Keywords: hydrogen sulfide, thiols, extraction, N-methylpyrrolidone, ultrasonic and magnetic treatment, microwave, redox activation


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