Steam reforming sulfur

In general, the proven technology to upgrade methane is via steam reforming to produce synthesis gas, CO + Such a gas mixture is clean and when converted to Hquids produces fuels substantially free of heteroatoms such as sulfur and nitrogen. Two commercial units utilizing the synthesis gas from natural gas technology in combination with novel downstream conversion processes have been commercialized. 

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... 

Steam Reforming Processes. In the steam reforming process, light hydrocarbon feedstocks (qv), such as natural gas, Hquefied petroleum gas, and naphtha, or in some cases heavier distillate oils are purified of sulfur compounds (see Sulfurremoval and recovery). These then react with steam in the presence of a nickel-containing catalyst to produce a mixture of hydrogen, methane, and carbon oxides. Essentially total decomposition of compounds containing more than one carbon atom per molecule is obtained (see Ammonia Hydrogen Petroleum). 

Steam reforming is the reaction of steam with hydrocarbons to make town gas or hydrogen. The first stage is at 700 to 830°C (1,292 to 1,532°F) and 15-40 atm (221 to 588 psih A representative catalyst composition contains 13 percent Ni supported on Ot-alumina with 0.3 percent potassium oxide to minimize carbon formation. The catalyst is poisoned by sulfur. A subsequent shift reaction converts CO to CO9 and more H2, at 190 to 260°C (374 to 500°F) with copper metal on a support of zinc oxide which protects the catalyst from poisoning by traces of sulfur. 

After the removal of sulfur, the primary steam reformer eonverts about 70% of the hydroearbon feed into synthesis gas. Methane is mixed with steam and passed over a niekel eatalyst. The main reforming reaetions are ... 

Figure 8.3.1 is a typical process diagram for tlie production of ammonia by steam reforming. Tlie first step in tlie preparation of tlie synthesis gas is desulfurization of the hydrocarbon feed. Tliis is necessary because sulfur poisons tlie nickel catalyst (albeit reversibly) in tlie reformers, even at very low concentrations. Steam reforming of hydrocarbon feedstock is carried out in tlie priiiiiiry and secondary reformers. 

Natural gas consists mainly of methane together with some higher hydrocarbons (Tab. 8.1). Sulfur, if present, must be removed to a level of about 0.2 ppm prior to the steam reforming process as it poisons the catalyst. This is typically done by cata-lytically converting the sulfur present as thiols, thiophenes or COS into H2S, which is then adsorbed stochiometrically by ZnO, at 400 °C, upstream of the reactor. 

It is important to note that the selectivity of sulfur-passivated catalysts towards steam reforming is greatly enhanced because carbon formation is effectively suppressed. The decrease in activity can to largely be compensated for by selecting inherently more active catalysts and by operating at higher temperatures. Unfortun-... 

Nickel catalysts used in steam reforming are more resistant to deactivation by carbon deposition if the surface contains sulfur, or gold. Explain why these elements act as promoters. Would you prefer sulfur or gold as a promoter Explain your answer. 

In the 1930s, Standard Oil of New Jersey (7) was the first company to employ on a commercial scale the indirect conversion of methane, the main component of natural gas, via steam reforming to give synthesis gas, which is a mixture of H2 and CO, with the H2/CO ratio depending on the reactant composition. C02 is also formed in synthesis gas production, and sulfur compounds are present as impurities. Synthesis gas can be used as a feedstock for numerous chemicals and fuels and as a source of pure hydrogen or carbon monoxide. 

There are three major gas reformate requirements imposed by the various fuel cells that need addressing. These are sulfur tolerance, carbon monoxide tolerance, and carbon deposition. The activity of catalysts for steam reforming and autothermal reforming can also be affected by sulfur poisoning and coke formation. These requirements are applicable to most fuels used in fuel cell power units of present interest. There are other fuel constituents that can prove detrimental to various fuel cells. However, these appear in specific fuels and are considered beyond the scope of this general review. Examples of these are halides, hydrogen chloride, and ammonia. Finally, fuel cell power unit size is a characteristic that impacts fuel processor selection. 

Logistic fuels, such as jet and diesel fuels, are readily available, but a compact and effective way to remove sulfur from these fuels is needed for portable hydrogen production. Consequently, for most portable applications, it is likely that sulfur-free fuels, such as methanol, will be used. An additional advantage of methanol is that it is easier to activate at low temperatures than other hydrocarbons. Therefore, a portable hydrogen production unit based on methanol steam reforming would be simpler and less costly than other alternatives. Methanol can also be considered an energy carrier as an alternative to liquefied natural gas... 

The hydrogen manufacture process is relatively clean. In the steam reforming subprocess a potential waste source is the desulfurization unit, which is required for feedstock that has not already been desulfurized. This waste stream contains oil, sulfur compounds, and phenol. In the partial oxidation subprocess, free carbon is removed by a water wash. Carbon dioxide is discharged to the atmosphere at several points in the subprocess. 

In addition to the direct use of ethanol as a fuel, its use as a source of H2 to be used with high efficiency in fuel cells has been thoroughly investigated. H2 production from ethanol has advantages compared vdth other H2 production techniques, including steam reforming of hydrocarbons and methanol. Unlike hydrocarbons, ethanol is easier to reform and is also free of sulfur, which is a well-known catalyst poison. Furthermore, unlike methanol, ethanol is completely renewable and has lower toxicity. 

Fixed- or packed-bed reactors refer to two-phase systems in which the reacting fluid flows through a tube filled with stationary catalyst particles or pellets (Smith, 1981). As in the case of ion-exchange and adsorption processes, fixed bed is the most frequently used operation for catalysis (Froment and Bischoff, 1990 Schmidt, 2005). Some examples in the chemical industry are steam reforming, the synthesis of sulfuric acid, ammonia, and methanol, and petroleum refining processes such as catalytic reforming, isomerization, and hydrocracking (Froment and Bischoff, 1990). 

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