Sulfur contents

Sulfur is present in petroleum as sulfides, thiophenes, benzothiophenes, and dibenzothiophenes. In most cases, the presence of sulfur is detrimental to the processing because sulfur can act as catalytic poisons during processing. 

The sulfur content of petroleum is an important property and varies widely within the rough limits 0.1% w/w to 3.0% w/w, and a sulfur content up to 8.0% w/w has been noted for tar sand bitumen. Compounds containing this element are among the most undesirable constituents of petroleum because they can give rise to plant corrosion and atmospheric pollution. Petroleum can evolve hydrogen sulfide during distillation as well as low-boUing sulfur compounds. 

A considerable number of tests are available to estimate the sulfur in petroleum or to study its effect on various products. Hydrogen sulfide dis- 

The Doctor test measures the amount of sulfur available to react with metallic surfaces at the temperature of the test. The rates of reaction are metal type-, temperature-, and time dependent. In the test, a sample is treated with copper powder at 149°C or 300°F. The copper powder is filtered from the mixture. Active sulfur is calculated from the difference between the sulfur contents of the sample (ASTM D-129) before and after treatment with copper. 

Until recently, one of the most widely used methods for determination of total sulfur content has been combustion of a sample in oxygen to convert the sulfur to sulfur dioxide, which is collected and subsequently titrated iodometricaUy or detected by nondispersive infrared (ASTM D-1552). This method is particularly applicable to heavier oil and fractions such as residua that boil above 177°C (350°F) and contain more than 0.06% w/w sulfur. In addition, the sulfur content of petroleum coke containing up to 8% w/w sulfur can be determined. 

Organic sulfur-bearing fluids ( r 0.1 wt%) corrode steel at high temperature. Based on accumulated experience in actual plant design. Chromium-molybdenimi steel is normally employed instead of carbon steel for the parts, where the operating temperature requires it. 

A serious erosion problem may arise around HDS piping and effluent air coolers downstream of the water injection point. Materials and fluid velocity should be determined by R.L. Piehls method. 

Several methods of sulfur determination are used for carbon black. They include oxygen bomb calorimetry, high-temperature combustion with an iodometric detection procedure and an infrared detection procedure. The results are given as percentage of sulfur. 

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Knowledge of sulfur content in petroleum products is imperative the analytical methods are numerous and depend on both the concentration being measured and the material being analyzed. 

Using this concept, Burdett developed a method in 1955 to obtain the concentrations in mono-, di- and polynuclear aromatics in gas oils from the absorbances measured at 197, 220 and 260 nm, with the condition that sulfur content be less than 1%. Knowledge of the average molecular weight enables the calculation of weight per cent from mole per cent. As with all methods based on statistical sampling from a population, this method is applicable only in the region used in the study extrapolation is not advised and usually leads to erroneous results. 

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. 

Hydrocracking makes very good quality diesel fuels concerning the cetane number, cold behavior, stability, and sulfur content. However this type of stock is only available in limited quantities since the process is still not widely used owing essentially to its high cost. 

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). 

Outside of their very high resistance to auto-ignition, the aviation gasolines are characterized by the following specifications vapor pressure between 385 and 490 mbar at 37.8°C, a distillation range (end point less than 170°C), freezing point (-60°C) and sulfur content of less than 500 ppm. 

Following 1 October 1996, diesel fuel should be desulfurized to a level of 0.05% while the maximum sulfur content of home-heating oils will stay provisionally at 0.2 %. 

In France there are four categories of heavy fuels whose specifications are given in Table 5.19 the different product qualities are distinguished essentially by the viscosity, equal to or less than 110 mm /s at SOT for No. 1 fuel oil, equal to or greater than 110 mm /s for No. 2 fuel oil, and by the sulfur content varying from 4 wt. % (No. 2 fuel oil) to 1 wt. % (No. 2 TBTS - very low sulfur content fuel oil). 

BTS Low sulfur content. TBTS Very low sulfur content. 

There are formulas for determining the NHV of heavy fueis as function of their density and their sulfur content. The simplest is the following ( /ifj... 

For the refiner, the main problem is to meet the specifications for kinematic viscosity and sulfur content. Dilution by light streams such as home-heating oil and LCO, and selection of feedstocks coming from low-sulfur crude oils give him a measure of flexibility that will nevertheless lead gradually to future restrictions, most notably the new more severe antipollution rules imposing lower limits on sulfur and nitrogen contents. 

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. 

It is noteworthy, however, that traces of sulfur can have beneficial effects on the anti-wear resistance of fuel injection pumps. It is thus undesirable to reduce the sulfur content to extremely low values unless additives having lubricating qualities are added. Independently from total sulfur content, the presence of mercaptans that are particularly aggressive towards certain metal or synthetic parts is strictly controlled. The mercaptan content is thereby limited to 0.002% (20 ppm) maximum. The analysis is performed chemically in accordance to the NF M 07-022 or ASTM D 3227 procedures. 

In the past, reducing the sulfur content was mainly concerned with the heaviest products, most particularly the fuel oils. This development is explained by a legitimate concern to reduce SO2 emissions, notably in areas around large population centers. This is how low sulfur heavy fuels —having a maximum of 2% sulfur— and very low sulfur ( % sulfur) came into being. Currently the whole range of petroleum products, particularly motor fuels, should be strongly desulfurized for reasons we will explain hereafter. 

Influence of sulfur content in gasoline (from 500 to 50 ppm) in the reduction of pollutant emissions. j... 

We have previously stated that the sulfur content of diesel fuel will be limited in Europe to 0.2% as of 1 October 1994 and to 0.05% as of 1 October 1996. 

The main justification for diesel fuel desulfurization is related to particulate emissions which are subject to very strict rules. Part of the sulfur is transformed first into SO3, then into hydrated sulfuric acid on the filter designed to collect the particulates. Figure 5.21 gives an estimate of the variation of the particulate weights as a function of sulfur content of diesel fuel for heavy vehicles. The effect is greater when the test cycle contains more high temperature operating phases which favor the transformation of SO2 to SO3. This is particularly noticeable in the standard cycle used in Europe (ECE R49). 

Desulfurization will become mandatory when oxidizing catalysts are installed on the exhaust systems of diesel engines. At high temperatures this catalyst accelerates the oxidation of SO2 to SO3 and causes an increase in the weight of particulate emissions if the diesel fuel has not been desulfurized. As an illustrative example, Figure 5.22 shows that starting from a catalyst temperature of 400°C, the quantity of particulates increases very rapidly with the sulfur content. 

Influence of the sulfur content in diesel fuel on particulate emissions as a, function of the catalytic converter inlet temperature. 

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. 

FOL No. 2 which can require supplementary specifications such as BTS (Low Sulfur content) and TBTS (Very Low Sulfur content). See AFNOR information documents M 15-010, M 15-011, M 15-012, M 15-013. 

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