Iron sulfides

In the 1950 s, crude oils were either corrosive (sour), or non-corrosive (sweet). Crudes containing more than 6 ppm of dissolved H2S were classed as sour because, beyond this limit, corrosion was observed on the walls of storage tanks by formation of scales of pyrophoric iron sulfides. 

Several iron sulfide nitrosyl compounds are known. These have stmctures that in some cases are formally related to the FeS clusters by replacement of thiolate by NO. The compounds include the anions [Fe2S2(NO)4] and [Fe4S2(NO)2] (Roussin s red and black salts, respectively) and the neutral compounds [Fe2S2(NO)4] and [Fe4S4(NO)4]. Roussin s black salt has found use as a NO releasing vasodilator. 

Depressants are reagents that selectively prevent the reaction between a coUector and a mineral, thus preventing its flotation. For example, sodium cyanide [143-33-9] depresses sphalerite [12169-28-7] (zinc sulfide) and pyrite [1309-36-0] (iron sulfide) but not galena. It thus enhances selective flotation of the galena. 

Manufacture. Small cylinders of hydrogen sulfide are readily available for laboratory purposes, but the gas can also be easily synthesized by action of dilute sulfuric or hydrochloric acid on iron sulfide, calcium sulfide [20548-54-3], zinc sulfide [1314-98-3], or sodium hydrosulfide [16721 -80-5]. The reaction usually is mn in a Kipp generator, which regulates the addition of the acid to maintain a steady hydrogen sulfide pressure. Small laboratory quantities of hydrogen sulfide can be easily formed by heating at 280—320°C a mixture of sulfur and a hydrogen-rich, nonvolatile aUphatic substance, eg, paraffin. Gas evolution proceeds more smoothly if asbestos or diatomaceous earth is also present. 

Shipment nd Stora.ge, Sulfur monochloride is minimally corrosive to carbon steel and iron when dry. If it is necessary to avoid discoloration caused by iron sulfide formation or chloride stress cracking, 310 stainless steel should be used. Sulfur monochloride is shipped in tank cars, tank tmcks, and steel dmms. When wet, it behaves like hydrochloric acid and attacks steel, cast iron, aluminum, stainless steels, copper and copper alloys, and many nickel-based materials. Alloys of 62 Ni—28 Mo and 54 Ni—15 Cr—16 Mo are useful under these conditions. Under DOT HM-181 sulfur monochloride is classified as a Poison Inhalation Hazard (PIH) Zone B, as well as a Corrosive Material (DOT Hazard Class B). Shipment information is available (140). 

Hydrogen sulfide reacts with iron oxide [1317-61 -9] to form iron sulfide, according to the following chemical reaction ... 

The sulfur is thus removed from the gas stream and trapped in the sorbent as iron sulfide [1317-37-9]. Over time all of the iron oxide becomes sulfided and the adsorptive capacity of the sorbent becomes exhausted. The bed can be partially regenerated by oxidation, as follows ... 

Iron Precipitation. Rich sulfide ore or Hquated antimony sulfide (cmde antimony) is reduced to metal by iron precipitation. This process, consisting essentially of heating molten antimony sulfide ia cmcibles with slightly more than the theoretical amount of fine iron scrap, depends on the abihty of iron to displace antimony from molten antimony sulfide. Sodium sulfate and carbon are added to produce sodium sulfide, or salt is added to form a light fusible matte with iron sulfide and to faciHtate separation of the metal. Because the metal so formed contains considerable iron and some sulfur, a second fusion with some Hquated antimony sulfide and salt foHows for purification. 

The disadvantage of this procedure is that the minerals maybe physically or chemically altered during burning. Eor example, the refractive index of clay minerals is changed the color, birefringence, and pleochroism of micas is altered carbonates are destroyed and the iron sulfides are oxidized to iron oxides. 

Potential Processes. Sulfur vapor reacts with other hydrocarbon gases, such as acetjiene [74-86-2] (94) or ethylene [74-85-1] (95), to form carbon disulfide. Higher hydrocarbons can produce mercaptan, sulfide, and thiophene intermediates along with carbon disulfide, and the quantity of intermediates increases if insufficient sulfur is added (96). Light gas oil was reported to be successflil on a semiworks scale (97). In the reaction with hydrocarbons or carbon, pyrites can be the sulfur source. With methane and iron pyrite the reaction products are carbon disulfide, hydrogen sulfide, and iron or iron sulfide. Pyrite can be reduced with carbon monoxide to produce carbon disulfide. 

The SRC-II process, shown in Figure 2, was developed in order to minimise the production of soHds from the SRC-I coal processing scheme. The principal variation of the SRC-II process relative to SRC-I was incorporation of a recycle loop for the heavy ends of the primary Hquefaction process. It was quickly realized that minerals which were concentrated in this recycle stream served as heterogeneous hydrogenation catalysts which aided in the distillate production reactions. In particular, pyrrhotites, non stoichiometric iron sulfides, produced by reduction of iron pyrite were identified as being... 

Furthermore, sulfur combines with copper rather than with iron. Hence, copper sulfide remains ia the converter after the iron has been oxidized and has combiaed with siUca to be skimmed off as a slag. Typical converting reactions of iron sulfide are equations 11, 14, and 15. 

Although it is not a catalytic process, the roasting of iron sulfide in fluidized beds at 650 to 1,100°C (1,202 to 2,012°F) is analogous. The pellets are 10-mm (0.39-in) diameter. There are numerous ants, but they are threatened with obsolescence because cheaper sources of sulfur are available for making sulfuric acid. 

FIG. 23-43 Reactors for solids, (a) Temperature profiles in a rotary cement lain, (h) A multiple hearth reactor, (c) Vertical lain for lime burning, 55 ton/d. (d) Five-stage fluidized bed lime burner, 4 by 14 m, 100 ton/d. (e) A fluidized bed for roasting iron sulfides. (/) Conditions in a vertical moving bed (blast furnace) for reduction of iron oxides, (g) A mechanical salt cake furnace. To convert ton/d to kg/h, multiply by 907. 

The manner in which many of these bacteria cany on their chemical processes is qmte comphcated and in some cases not fuUy understood. The role of sulfate-reducing bacteria (anaerobic) in promoting corrosion has been extensively investigated. The sulfates in shghtly acid to alkaline (pH 6 to 9) soils are reduced by these bacteria to form calcium sulfide and hydrogen sulfide. When these compounds come in contact with underground iron pipes, conversion of the iron to iron sulfide occurs. As these bacieria thrive under these conditions, they will continue to promote this reaction until failure of the pipe occurs. 

Sulfides are intermixed with iron oxides and hydroxides on carbon steels and cast irons. The oxides are also produced in the corrosion process (Reaction 6.6). Although theoretical stoichiometry of 1 to 3 is often suggested between sulfide and ferrous hydroxide, empirically the ratio of iron sulfide to ferrous hydroxide is highly variable. Sulfide decomposes spontaneously upon exposure to moist air. Additionally, corrosion-product stratification is marked, with sulfide concentration being highest near metal surfaces. 

Stainless steels attacked by sulfate reducers show well-defined pits containing relatively little deposit and corrosion product. On freshly corroded surfaces, however, black metal sulfides are present within pits. Rust stains may surround pits or form streaks running in the direction of gravity or flow from attack sites. Carbon steel pits are usually capped with voluminous, brown friable rust mounds, sometimes containing black iron sulfide plugs fFig. 6.10). 

The weld was riddled with mildly undercut, gaping pits. Attack was confined to fused and heat-affected zones, with a pronounced lateral or circumferential propagation (as in Fig. 6.10). The resulting perforation at the external surface was quite small. Pits were filled with deposits, friable oxides, and other corrosion products. Black plugs embedded in material filling the gaping pit contained high concentrations of iron sulfide. Bulk deposits contained about 90% iron oxide. Carbonaceous material was not detected. 

Homogeneous galvanic corrosion may also occur on the surface of steel components that are covered or partially covered with mill scale (magnetite, Fe304) or iron sulfide corrosion products. Both mill scale and iron sulfide are noble with respect to steel. Significant galvanic corrosion can occur where breaks or holidays in these corrosion products expose unprotected metal. 

Note that nonmetallic substances such as mill scale (Fe304) and iron sulfide (FeaS) are not listed. Nevertheless, on the surface of steel these substances can produce galvanic corrosion of the steel due to their relatively noble character. 

Ahrens, T.J. (1979), Equations of State of Iron Sulfide and Constraints on the Sulfur Content of the Earth, J. Geophys. Res. 84, 985-998. 

A relatively high degree of corrosion arises from microbial reduction of sulfates in anaerobic soils [20]. Here an anodic partial reaction is stimulated and the formation of electrically conductive iron sulfide deposits also favors the cathodic partial reaction. 

Regeneration with air can be done with continuous or periodic addition of small amounts of air. Both must be done carefully because of exothermic reaction. Regeneration is never complete, so the beds must be eventually changed out. This must be done carefully because of the pyrophoric (spontaneously combustible) nature of the iron sulfide. The entire bed is wetted first. 

---