Sulfur content of products

Hydrotreating reduces the sulfur content of product streams from sour crudes by 90% or more. Nitrogen removal requires more severe operating conditions, but generally 80% reductions or better are accomplished. 

The refinery mass balance of Table 5 shows a decisive shift to high-sulfur crude in the future increasing the total intake of high-sulfur crudes from 63 to 84% of total feed. Nonetheless, the refinery SOj emissions and the sulfur content of products are both reduced by one-third, as can seen in Table 6. Similar reductions can be seen for NO ... 

Until 1992, the total sulfur content of jet fuel was limited to 0.2 wt. %. Starting in 1993, a reduction to 0.1% was instituted apparently without major incident since for commercial products, lower levels (to 500 ppm) had been observed very often. 

The volatiles contents of product chars decreased from ca 25—16% with temperature. Char (lower) heating values, on the other hand, increased from ca 26.75 MJ /kg (11,500 Btu/lb) to 29.5 MJ /kg (12,700 Btu/lb) with temperature. Chars in this range of heating values are suitable for boiler fuel apphcation and the low sulfur content (about equal to that of the starting coal) permits direct combustion. These char products, however, are pyrophoric and require special handling in storage and transportation systems. 

The quahty of naphthalene required for phthaUc anhydride manufacture is generally 95% minimum purity. The fixed plants do not require the high (>98%) purity naphthalene product and low (<50 ppm) sulfur. The typical commercial coal-tar naphthalene having a purity ca 95% (freezing point, 77.5°C), a sulfur content of ca 0.5%, and other miscellaneous impurities, is acceptable feedstock for the fixed-bed catalyst process based on naphthalene. 

The significance of the total sulfur content of kerosene varies greatly with the type of oil and the use to which it is put. Sulfur content is of great importance when the kerosene to be burned produces sulfur oxides, which are of environmental concern. The color of kerosene is of Htde significance but a product darker than usual may have resulted from contamination or aging in fact, a color darker than specified may be considered by some users as unsatisfactory. Kerosene, because of its use as a burning oil, must be free of aromatic and unsaturated hydrocarbons the desirable constituents of kerosene are saturated hydrocarbons. 

Trinidad asphalt has a relatively uniform composition of 29% water and gas, 39% bitumen soluble in carbon disulfide, 27% mineral matter on ignition, and 5% bitumen that remains adsorbed on the mineral matter. Refining is essentially a process of dehydration by heating the cmde asphalt to ca 165°C. The refined product averages 36% mineral ash with a penetration at 25°C of about 2 (0.2 mm), a softening point (ring and ball method) of 99°C, a flash point (Cleveland open cup) of 254°C, a sulfur content of 3.3%, and a saponification value of 45 mg KOH/g. The mineral matter typically contains... 

Mercaptan extraction is used to reduce the total sulfur content of the fuel. When potassium isobutyrate and sodium cresylate are added to caustic soda, the solubility of the higher mercaptans is increased and they can be extracted from the oil. To remove traces of hydrogen sulfide and alkyl phenols, the oil is pretreated with caustic soda in a packed column or other mixing device. The mixture is allowed to settle and the product water washed before storage. 

Hydrotreating reduces the sulfur content of all the products. With hydrotreated feeds, more of the feed sulfur goes to coke and heavy liquid products. The same sulfur atoms that were converted to H S in the FCC process are also being removed first in the hydrotreating process. The remaining sulfur compounds are harder to remove. The heavier and more aromatic the feedstock, the greater the level of sulfur in the coke (Table 2-7). 

Desulfurization of FCC feedstocks reduces the sulfur content of FCC products and SOX emissions. In the United States, road diesel sulfur can be 500 ppm (0.05 wt%). In some European countries, for example in Sweden, the sulfur of road diesel is 50 ppm or less. In California, the gasoline sulfur is required to be less than 40 ppm. The EPA s complex model uses sulfur as a controlling parameter to reduce toxic emissions. With hydroprocessed FCC feeds, about 5% of feed sulfur is in the FCC gasoline. For non-hydroprocessed feeds, the FCC gasoline sulfur is typically 10% of the feed sulfur. 

Although an increase in the sulfur content of the residue feedstock will have a minimal effect on unit yields, the sulfur content of the RFCC products and the flue gas is greater, requiring additional treating facilities. 

Feed hydrotreating or hydrocracking reduces SOj, emissions and the sulfur content of FCC products. As discussed earlier in this chapter, many benefits are associated with FCC feed hydrotreating. It is important to note that most of the sulfur in a hydrotreated feed is in heavy organic compounds and will be concentrated in the decanted oil and coke. Consequently, for a given sulfur in the feed, more SO, will be produced with hydrotreated feed. 

Four variables were studied in the part of the experimental program which examined the first step of the proposed two-step process. The variables were reaction temperature (413-454 C), solvent to coal ratio (2 1 and 3 1), residence time (0-5 minutes), and pressure (300-1800 psi nitrogen). Four experiments were done to simulate the second step, in which hydrogenated solvent and molecular hydrogen would be used to lower the sulfur content of the product. These experiments were done at 441 C for 2 minutes, with and without molecular hydrogen and recycle solvent containing 25 weight percent Tetralin. 

Saniter A modification of the Basic Open Hearth process for reducing the sulfur content of the steel product by adding relatively large quantities of limestone and calcium chloride. Invented by E. H. Saniter at the Wigan Coal Iron Company in England in 1892, and used there and in Germany for approximately 20 years until superseded by the use of calcium fluoride as a flux. 

The phase Na2Sx is sodium polysulfide, a material with a sulfur content of between 3 and 5. The anode reaction takes place at the liquid sodium - (3"-alununa interface. Here sodium atoms lose an electron and the Na+ ions formed enter the conduction planes in the electrolyte. The cathode reaction, which occurs at the interface between the (3"-alumina and the liquid sulfur forms sodium polysulfides. Despite the desirable properties of the cell, technical and economic considerations have acted so as to curtail large-scale commercial production. 

Assuming that demand for petroleum continues to increase at a rate of 1.2% per annum to 2010,37 and that all gasoline and diesel produced by U.S. refineries will have a sulfur content of less than 30 ppm, desulfurization of gasoline and diesel to these low levels will require extensive hydrotreating of both catalytic cracker feed and product of distillate. 

Figure 14.2 shows that the production of 99% pure hydrogen requires many catalytic processes. The desulfurization section is used to reduce the sulfur content of the natural gas to 0.01 ppm to protect the SMR and WGS catalysts downstream. A supported cobalt-molybdenum catalyst (CoMoS) converts the sulfur compounds into H2S, which is removed by a ZnO catalyst [5]. 

Unfortunately, pyrite sulfur makes up only half the sulfur content of coal, while the other half is organically bound. Coal gasification is the only means by which this sulfur mode can be removed. Of course, it is always possible to eliminate the deleterious effects of sulfur by removing the major product oxide S02 by absorption processes. These processes impose large initial capital investments. 

In the iodate detection system (ASTM D1552), the sample is burned in a stream of oxygen at a sufficiently high temperature to convert about 97% by weight of the sulfur to sulfur dioxide. The combustion products are passed into an absorber containing an acidic solution of potassium iodide and starch indicator. A faint blue color is developed in the absorber solution by the addition of standard potassium iodate solution. As combustion proceeds, bleaching the blue color, more iodate is added. The sulfur content of the sample is calculated from the amount of standard iodate consumed during the combustion. 

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