Sulfur advantages

The potential advantages of LPG concern essentially the environmental aspects. LPG s are simple mixtures of 3- and 4-carbon-atom hydrocarbons with few contaminants (very low sulfur content). LPG s contain no noxious additives such as lead and their exhaust emissions have little or no toxicity because aromatics are absent. This type of fuel also benefits often enough from a lower taxation. In spite of that, the use of LPG motor fuel remains static in France, if not on a slightly downward trend. There are several reasons for this situation little interest from automobile manufacturers, reluctance on the part of automobile customers, competition in the refining industry for other uses of and fractions, (alkylation, etherification, direct addition into the gasoline pool). However, in 1993 this subject seems to have received more interest (Hublin et al., 1993). 

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. 

Clearly, it is important that there be a large contact angle at the solid particle-solution-air interface. Some minerals, such as graphite and sulfur, are naturally hydrophobic, but even with these it has been advantageous to add materials to the system that will adsorb to give a hydrophobic film on the solid surface. (Effects can be complicated—sulfur notability oscillates with the number of preadsoibed monolayers of hydrocarbons such as n-heptane [76].) The use of surface modifiers or collectors is, of course, essential in the case of naturally hydrophilic minerals such as silica. 

The Peterson reaction has two more advantages over the Wittig reaction 1. it is sometimes less vulnerable to sterical hindrance, and 2. groups, which are susceptible to nucleophilic substitution, are not attacked by silylated carbanions. The introduction of a methylene group into a sterically hindered ketone (R.K. Boeckman, Jr., 1973) and the syntheses of olefins with sulfur, selenium, silicon, or tin substituents (D. Seebach, 1973 B.T. Grdbel, 1974, 1977) illustrate useful applications. The reaction is, however, more limited and time consuming than the Wittig reaction, since metallated silicon derivatives are difficult to synthesize and their reactions are rarely stereoselective (T.H. Chan, 1974 ... 

Methanol, a clean burning fuel relative to conventional industrial fuels other than natural gas, can be used advantageously in stationary turbines and boilers because of its low flame luminosity and combustion temperature. Low NO emissions and virtually no sulfur or particulate emissions have been observed (83). Methanol is also considered for dual fuel (methanol plus oil or natural gas) combustion power boilers (84) as well as to fuel gas turbines in combined methanol / electric power production plants using coal gasification (85) (see Power generation). 

Ca.ta.lysis by Protons. The discovery of hydrogen peroxide hydroxylation of phenol in the presence of strong acids such as perchloric, trifluoromethane-sulfonic, or sulfuric acids allows suppression of all previous drawbacks of the process (18,19). This mode of hydroxylation gives high yields (85% based on H2O2 at phenol conversion of 5—6%). It can be mn without solvents and does not generate resorcinol. Its main advantage rehes on... 

Sulfur Compounds. Various gas streams are treated by molecular sieves to remove sulfur contaminants. In the desulfurization of wellhead natural gas, the unit is designed to remove sulfur compounds selectively, but not carbon dioxide, which would occur in Hquid scmbbing processes. Molecular sieve treatment offers advantages over Hquid scmbbing processes in reduced equipment size because the acid gas load is smaller in production economics because there is no gas shrinkage (leaving CO2 in the residue gas) and in the fact that the gas is also fliUy dehydrated, alleviating the need for downstream dehydration. 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

In the last few years several modifications to the traditional mixed acid nitration procedure have been reported. An adiabatic nitration process was developed for the production of nitrobenzene (9). This method eliminated the need to remove the heat of reaction by excessive cooling. The excess heat can be used in the sulfuric acid reconcentration step. An additional advantage of this method is the reduction in reaction times to 0.5—7.5 minutes. 

Another concentration method involves passing an inert gas such as N2 or CO2 through the reaction medium (12). As the gas passes through, it becomes humidified and carries captured water with it. Most of the energy required for the gas humidification comes from the heat of reaction. An advantage is that expensive drying equipment is not needed. Also, the sulfuric acid mist formed in typical concentrators is minimized. Du Pont uses a similar process in its nitrobenzene production faciUty. 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

Acid Treatment. The treatment of petroleum products with acids has been in use for a considerable time in the petroleum industry. Various acids such as hydrofluoric acid, hydrochloric acid, nitric acid, and phosphoric acid have been used in addition to the most commonly used sulfuric acid, but in most instances there is Httie advantage in using any acid other than sulfuric. 

These catalysts contained promoters to minimise SO2 oxidation. Second-generation systems are based on a combined oxidation catalyst and particulate trap to remove HC and CO, and to alleviate particulate emissions on a continuous basis. The next phase will be the development of advanced catalysts for NO removal under oxidising conditions. Low or 2ero sulfur diesel fuel will be an advantage in overall system development. 

Semichemical pulping can be accompHshed by a sulfur-free system of sodium hydroxide and sodium carbonate. The sodium carbonate is recovered by simple incineration, and sodium hydroxide is added as makeup. Advantages in recovery operation are obtained if potassium hydroxide is added occasionally to maintain ca 20 mol % potassium carbonate (66). Lastiy, semichemical pulping can be accompHshed by using kraft white Hquor of low strength. 

Esterification is frequendy carried out by direct reaction of the carboxyhc acid with an alcohol in the presence of a small amount of mineral acid, usually concentrated sulfuric or hydrochloric acid. The esters of commercial importance in both 0- and -hydroxyben2oic acid are the methyl esters. Direct esterification has the advantage of being a single-step synthesis, but being an equihbrium it is easily reversed. The reaction to the ester is driven by either of... 

One more variation to the many methods proposed for sulfur extraction is the fire-flood method. It is a modem version of the Sickian method, by which a portion of the sulfur is burned to melt the remainder. It would be done in situ and is said to offer cost advantages, to work in almost any type of zone formation, and to produce better sweep efficiency than other systems. The recovery stream would be about 20 wt % sulfur as SO2 and 80 wt % elemental sulfur. The method was laboratory-tested in the late 1960s and patents were issued. However, it was not commercially exploited because sulfur prices dropped. 

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