Sulfur desulfurization

Schwefel-einschlag, m. sulfur match (for casks) sulfuring (of casks), eisen, n. iron sulfide (usiially ferrous sulfide, Iron(II) sulfide), -entfernung,/. removal of sulfur, desulfurization. -erz, n. sulfur ore. -faden, m. sulfured wick, sulfur match, -farbe, /. sulfur color sulfur dye (of wool) stoved shade. 

Involving extraction with aqueous sodium carbonate solution (16). This loss of oxygen probably Involves an oxathliran intermediate 18 which can also extrude sulfur. Desulfuration to form the thio-carbamate (. . 12)is normally a minor pathway but becomes major... 

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 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. 

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. 

Finally, sulfur has a negative effect on the performance of the catalyst itself. One sees for example in Figure 5.23 that the initiation temperature increases with the sulfur level in the diesel fuel, even between 0.01% and 0.05%. Yet, in the diesel engine, characterized by relatively low exhaust temperatures, the operation of the catalyst is a determining factor. One can thus predict an ultimate diesel fuel desulfurization to levels lower than 0.05%. 

The European regulations have set SO2 emission limits for industrial combustion systems. They range from 1700 mg/Nm for power generation systems of less than 300 MW and to 400 mg/Nm for those exceeding 500 MW between 300 and 500 MW, the requirements are a linear interpolation (Figure 5.24). To give an idea how difficult it is to meet these requirements, recall that for a fuel having 4% sulfur, the SO2 emissions in a conventional boiler are about 6900 mg/Nm this means that a desulfurization level of 75% will be necessary to attain the SO2 content of 1700 mg/Nm and a level of 94% to reach 400 mg/Nm. ... 

For example, in the case of light Arabian crude (Table 8.16), the sulfur content of the heavy gasoline, a potential feedstock for a catalytic reforming unit, is of 0.036 weight per cent while the maximum permissible sulfur content for maintaining catalyst service life is 1 ppm. It is therefore necessary to plan for a desulfurization pretreatment unit. Likewise, the sulfur content of the gas oil cut is 1.39% while the finished diesel motor fuel specification has been set for a maximum limit of 0.2% and 0.05% in 1996 (French specifications). 

The problem of the synthesis of highly substituted olefins from ketones according to this principle was solved by D.H.R. Barton. The ketones are first connected to azines by hydrazine and secondly treated with hydrogen sulfide to yield 1,3,4-thiadiazolidines. In this heterocycle the substituents of the prospective olefin are too far from each other to produce problems. Mild oxidation of the hydrazine nitrogens produces d -l,3,4-thiadiazolines. The decisive step of carbon-carbon bond formation is achieved in a thermal reaction a nitrogen molecule is cleaved off and the biradical formed recombines immediately since its two reactive centers are hold together by the sulfur atom. The thiirane (episulfide) can be finally desulfurized by phosphines or phosphites, and the desired olefin is formed. With very large substituents the 1,3,4-thiadiazolidines do not form with hydrazine. In such cases, however, direct thiadiazoline formation from thiones and diazo compounds is often possible, or a thermal reaction between alkylideneazinophosphoranes and thiones may be successful (D.H.R. Barton, 1972, 1974, 1975). 

Diallylsulfonium salts undergo intramolecular allylic rearrangement with strong bases to yield 1,5-dienes after reductive desulfurization. The straight-chain 1,5-dienes may be obtained by double sulfur extrusion with concomitant allylic rearrangements from diallyl disulfides. The first step is achieved with phosphines or phosphites, the second with benzyne. This procedure is especially suitable for the synthesis of acid sensitive olefins and has been used in oligoisoprene synthesis (G.M. Blackburn, 1969). 

The high nucleophilicity of sulfur atoms is preserved, even if it is bound to electron withdrawing carbonyl groups. Thiocarboxylales, for example, substitute bromine, e.g. of a-bromo ketones. In the presence of bases the or-acylthio ketones deprotonate and rearrange to episulfides. After desulfurization with triphenylphosphine, 1,3-diketones are formed in good yield. Thiolactams react in the same way, and A. Eschenmoser (1970) has used this sequence in his vitamin B]2 synthesis (p. 261). 

In 1874, Volhard (39) showed that thiohydantoin resisted desulfuration, proving its sulfur atom to be more firmly bonded than formula 34 indicated. 

The formation of a sulfur-containing ring was justified by the attack of the halogenated carbon of the cMoroacetyl derivative by the sulfur atom of thiourea, a fact in accordance with the results just discussed by Wallach (49,50) and Claus (51). The new formula (37) of thiohydantoine explained why, contrary to thiourea, its desulfuration was difficult. 

Active Raney nickel induces desulfurization of many sulfur-containing heterocycles thiazoles are fairly labile toward this ring cleavage agent. The reaction occurs apparently by two competing mechanisms (481) in the first, favored by alkaline conditions, ring fission occurs before desul-, furization, whereas in the second, favored by the use of neutral catalyst, the initial desulfurization is followed by fission of a C-N bond and formation of carbonyl derivatives by hydrolysis (Scheme 95). 

Sulfur Dioxide Processing, Repriuts of 1972—1974 Chem. Eng. Prog, articles, AIChE, New York (1975). Contaius thirteen papers on flue gas desulfurization, two on SO2 control iu pulp and paper, one on sulfuric acid tail gas, one on SO2 from ore roasting, and two on NO from nitric acid. 

Methanation of the clean desulfurized main gas (less than 1 ppm total sulfur) is accompHshed in the presence of a nickel catalyst at temperatures from 260—400°C and pressure range of 2—2.8 MPa (300—400 psi). Equations and reaction enthalpies are given in Table 4. 

Properties. The properties of char products from two possible coal feeds, a low sulfur Western coal, and a high sulfur Midwestern coal, are shown in Table 11. The char derived from the low sulfur Western coal may be direcdy suitable as plant fuel, with only minor addition of clean process gas to stabilize its combustion. Elue gas desulfurization may not be required. Elue gas from the combustion of the char derived from the high sulfur Illinois coal, however, requires desulfurization before it may be discharged into the atmosphere. 

Because hydrocarbon feeds for steam reforming should be free of sulfur, feed desulfurization is required ahead of the steam reformer (see Sulfur REMOVAL AND RECOVERY). As seen in Figure 1, the first desulfurization step usually consists of passing the sulfur-containing hydrocarbon feed at about 300—400°C over a Co—Mo catalyst in the presence of 2—5% H2 to convert organic sulfur compounds to H2S. As much as 25% H2 may be used if olefins... 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Fresh reducing gas is generated by reforming natural gas with steam. The natural gas is heated in a recuperator, desulfurized to less than 1 ppm sulfur, mixed with superheated steam, further preheated to 620°C in another recuperator, then reformed in alloy tubes filled with nickel-based catalyst at a temperature of 830°C. The reformed gas is quenched to remove water vapor, mixed with clean recycled top gas from the shaft furnace, reheated to 925°C in an indirect fired heater, and injected into the shaft furnace. For high (above 92%) metallization a CO2 removal unit is added in the top gas recycle line in order to upgrade the quaUty of the recycled top gas and reducing gas. 

In another development (32), the sodium sulfate solution produced during the desulfurization of paste with caustic soda is electrolyzed in a membrane ceU to produce caustic soda and high purity sulfuric acid. The caustic soda is recycled to the desulfurization stage the sulfuric acid, after concentration, can be reused in battery production. 

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. 

Since the original cmde oils contain some sulfur compounds, the resulting products and gasolines also contain sulfur compounds, including hydrogen sulfide, mercaptans, sulfides, disulfides, and thiophenes. The processes used to sweeten, ie, desulfurize, the products depend on the type and amount of the sulfur compounds present and the specifications of the finished gasoline or other stocks. 

One method for using sodium alumiaate to desulfurize flue gas containing sulfur dioxide is described (45). This procedure led to a process where aluminum sulfate [10043-01-3] could be generated as a by-product of flue gas desulfurization (46). 

Emissions control systems play an important role at most coal-fired power plants. For example, PC-fired plants sited in the United States require some type of sulfur dioxide control system to meet the regulations set forth in the Clean Air Act Amendments of 1990, unless the boiler bums low sulfur coal or benefits from offsets from other highly controlled boilers within a given utiUty system. Flue-gas desulfurization (FGD) is most commonly accomphshed by the appHcation of either dry- or wet-limestone systems. Wet FGD systems, also referred to as wet scmbbers, are the most effective solution for large faciUties. Modem scmbbers can typically produce a saleable waUboard-quaUty gypsum as a by-product of the SO2 control process (see SULFURREMOVAL AND RECOVERY). 

Naphthalene sodium prepared in dimethyl ether or another appropriate solvent, or metallic sodium dissolved in Hquid ammonia or dimethyl sulfoxide, is used to treat polyfluorocarbon and other resins to promote adhesion (138—140). Sodium, usually in dispersed form, is used to desulfurize a variety of hydrocarbon stocks (141). The process is most useful for removal of small amounts of sulfur remaining after hydrodesulfurization. 

In metallurgical practice, sodium uses include preparation of powdered metals removal of antimony, tin, and sulfur from lead modification of the stmcture of siHcon—aluminum alloys appHcation of diffusion alloy coatings to substrate metals (162,163) cleaning and desulfurizing alloy steels via NaH (164) nodularization of graphite in cast iron deoxidation of molten metals heat treatment and the coating of steel using aluminum or zinc. 

Other Uses. Other uses include intermediate chemical products. Overall, these uses account for 15—20% of sulfur consumption, largely in the form of sulfuric acid but also some elemental sulfur that is used directly, as in mbber vulcanization. Sulfur is also converted to sulfur trioxide and thiosulfate for use in improving the efficiency of electrostatic precipitators and limestone/lime wet flue-gas desulfurization systems at power stations (68). These miscellaneous uses, especially those involving sulfuric acid, are intimately associated with practically all elements of the industrial and chemical complexes worldwide. 

Sulfur Dioxide Emissions and Control. A substantial part of the sulfur dioxide in the atmosphere is the result of burning sulfur-containing fuel, notably coal, and smelting sulfide ores. Methods for controlling sulfur dioxide emissions have been reviewed (312—314) (see also Air POLLUTION CONTROL PffiTHODS COAL CONVERSION PROCESSES, CLEANING AND DESULFURIZATION EXHAUST CONTROL, INDUSTRIAL SULFURREMOVAL AND RECOVERY). 

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