Sulfur: characteristics

With respect to fuels utilized as heating fuels for industrial furnaces, or as motor fuels for large diesel engines such as those in ships or power generation sets, the characteristics of primary importance are viscosity, sulfur content and the content of extremely heavy materials (asphaltenes) whose combustion can cause high emissions of particulates which are incompatible with antipollution legislation. 

The high C/H ratio for heavy fuels and their high levels of contaminants such as sulfur, water, and sediment, tend to reduce their NHV which can reach as low as 40,000 kJ/kg by comparison to the 42,500 kJ/kg for a conventional home-heating oil. This characteristic is not found in the specifications, but it is a main factor in price negotiations for fuels in terms of cost per ton. Therefore it is subject to frequent verification. 

Characteristics Atmospheric residue (Arabian light) Vacuum residue (VR) Visbroken residue (on VR) LCO (low sulfur) HCO (low sulfur)... 

Table 5.28 gives the modifications in physical/chemical characteristics resulting from deeper and deeper hydrotreatment (Martin et al., 1992). The sulfur contents could thus be reduced to first as low as a few hundred ppm, then to a few ppm. The level of aromatics in the selected example drops from 39% to 7% while the cetane number increases from 49 to 60. Note here that such a treatment, possible through experimental means, does not correspond to current industrial practice because of its high cost and its very high hydrogen consumption. 

The different cuts obtained are collected their initial and final distillation temperatures are recorded along with their weights and specific gravities. Other physical characteristics are measured for the light fractions octane number, vapor pressure, molecular weight, PONA, weight per cent sulfur, etc., and, for the heavy fractions, the aniline point, specific gravity, viscosity, sulfur content, and asphaltene content, etc. 

It is possible to calculate the properties of wider cuts given the characteristics of the smaller fractions when these properties are additive in volume, weight or moles. Only the specific gravity, vapor pressure, sulfur content, and aromatics content give this advantage. All others, such as viscosity, flash point, pour point, need to be measured. In this case it is preferable to proceed with a TBP distillation of the wider cuts that correspond with those in an actual refinery whose properties have been measured. 

Hydrotreating processes are applied to finished products to improve their characteristics sulfur content, cetane number, smoke point and the aromatics and olefins contents. 

The organic chemical structural types believed to be characteristic of coals include complex polycyclic aromatic ring systems with connecting bridges and varied oxygen-, sulfur-, and nitrogen-containing functionalities. 

Type J thermocouples (Table 11.58) are one of the most common types of industrial thermocouples because of the relatively high Seebeck coefficient and low cost. They are recommended for use in the temperature range from 0 to 760°C (but never above 760°C due to an abrupt magnetic transformation that can cause decalibration even when returned to lower temperatures). Use is permitted in vacuum and in oxidizing, reducing, or inert atmospheres, with the exception of sulfurous atmospheres above 500°C. For extended use above 500°C, heavy-gauge wires are recommended. They are not recommended for subzero temperatures. These thermocouples are subject to poor conformance characteristics because of impurities in the iron. 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

Black Powder. Black powder is mainly used as an igniter for nitrocellulose gun propellant, and to some extent in safety blasting fuse, delay fuses, and in firecrackers. Potassium nitrate black powder (74 wt %, 15.6 wt % carbon, 10.4 wt % sulfur) is used for military appHcations. The slower-burning, less cosdy, and more hygroscopic sodium nitrate black powder (71.0 wt %, 16.5 wt % carbon, 12.5 wt % sulfur) is used industrially. The reaction products of black powder are complex (Table 12) and change with the conditions of initia tion, confinement, and density. The reported thermochemical and performance characteristics vary greatly and depend on the source of material, its physical form, and the method of determination. Typical values are Hsted in Table 13. 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Nitric Phosphate. About 15% of worldwide phosphate fertilizer production is by processes that are based on solubilization of phosphate rock with nitric acid iastead of sulfuric or phosphoric acids (64). These processes, known collectively as nitric phosphate or nitrophosphate processes are important, mainly because of the iadependence from sulfur as a raw material and because of the freedom from the environmental problem of gypsum disposal that accompanies phosphoric acid-based processes. These two characteristics are expected to promote eventual iacrease ia the use of nitric phosphate processes, as sulfur resources diminish and/or environmental restrictions are tightened. 

Sulfur hexafluoride [2551-62-4] 6 molecular weight 146.07, is a colorless, odorless, tasteless gas. It is not flammable and not particularly reactive. Its high chemical stabiUty and excellent electrical characteristics have led to widespread use in various kinds of electrical and electronic equipment such as circuit breakers, capacitors, transformers, microwave components, etc (see Electronic materials). Other properties of the gas have led to limited usage in a variety of unique appHcations ranging from medical appHcations to space research. 

Environmental considerations also were reflected in coal production and consumption statistics, including regional production patterns and economic sector utilization characteristics. Average coal sulfur content, as produced, declined from 2.3% in 1973 to 1.6% in 1980 and 1.3% in 1990. Coal ash content declined similarly, from 13.1% in 1973 to 11.1% in 1980 and 9.9% in 1990. These numbers clearly reflect a trend toward utilization of coal that produces less SO2 and less flyash to capture. Emissions from coal in the 1990s were 14 x 10 t /yr of SO2 and 450 x 10 t /yr of particulates generated by coal combustion at electric utiUties. The total coal combustion emissions from all sources were only slightly higher than the emissions from electric utiUty coal utilization (6). 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

Many types of stainless steels are available. The type most widely used in the dairy industry is 18—8 (18% chromium, 8% nickel plus iron). Small amounts of siHcon, molybdenum, manganese, carbon, sulfur, and phosphoms maybe included to obtain characteristics desired for specific appHcations. 

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

Naphthenic acids are viscous hquids, with phenohc and sulfur impurities present that are largely responsible for their characteristic odor. Their colors range from pale yeUow to dark amber. An odor develops upon storage of the refined acids. Naphthenic acids have wide boiling point ranges at high temperatures (250—350°C). They are completely soluble in organic solvents and oils but are insoluble (<50 mg/L) in water. Commercial naphthenic acids are available in... 

In the days of alchemy and the phlogiston theory, no system of nomenclature that would be considered logical ia the 1990s was possible. Names were not based on composition, but on historical association, eg, Glauber s salt for sodium sulfate decahydrate and Epsom salt for magnesium sulfate physical characteristics, eg, spirit of wiae for ethanol, oil of vitriol for sulfuric acid, butter of antimony for antimony trichloride, Hver of sulfur for potassium sulfide, and cream of tartar for potassium hydrogen tartrate or physiological behavior, eg, caustic soda for sodium hydroxide. Some of these common or trivial names persist, especially ia the nonchemical Hterature. Such names were a necessity at the time they were iatroduced because the concept of molecular stmcture had not been developed, and even elemental composition was incomplete or iadeterminate for many substances. 

The concentrated mother Hquor contains a large amount of sulfuric acid in a free form, as titanium oxy-sulfate, and as some metal impurity sulfates. To yield the purest form of hydrated TiOg, the hydrolysis is carried out by a dding crystallizing seeds to the filtrate and heating the mixture close to its boiling temperature, - 109° C. The crystal stmcture of the seeds (anatase or mtile) and their physical properties affect the pigmentary characteristics of the final product. 

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