Sulfur compounds hydrodesulfurization

Natural gas contains both organic and inorganic sulfur compounds that must be removed to protect both the reforming and downstream methanol synthesis catalysts. Hydrodesulfurization across a cobalt or nickel molybdenum—zinc oxide fixed-bed sequence is the basis for an effective purification system. For high levels of sulfur, bulk removal in a Hquid absorption—stripping system followed by fixed-bed residual clean-up is more practical (see Sulfur REMOVAL AND RECOVERY). Chlorides and mercury may also be found in natural gas, particularly from offshore reservoirs. These poisons can be removed by activated alumina or carbon beds. 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

Aj Hydrodesulfurization Removal of sulfur compounds from crude oil by reaction with hydrogen on CO - Mo on alumina. 

It should be noted, however, that this reaction sequence may be different from what may actually be occurring in the reactor. The reactions proceed at different rates depending on the process variables. Hydrodesulfurization of complex sulfur compounds such as dibenzothiophene also occurs under these conditions. The desulfurized product may crack to give two benzene molecules ... 

Although desulfurization is not the goal of cat cracking operations, approximately 50% of sulfur in the feed is converted to HjS. in addition, the remaining sulfur compounds in the FCC products are lighter and can be desulfurized by low-pressure hydrodesulfurization processing. 

The general reaction occurring in hydrodesulfurization has been described in Section 2.1.1. The most studied model compound is DBT. The reactivity towards hydrogenation of the phenyl substituents already mentioned (Section 2.1.1) is also observed in the hydroprocessing of sulfur compounds. The reactivity towards hydrogenolysis of the C-S bond masks the effects associated to aromatics hydrogenation. The DBT reaction network is sketched in Fig. 8 the pseudo-first-order reaction constants measured by Houalla [68] have been included. 

Autofining A fixed-bed catalytic process for removing sulfur compounds from petroleum distillates. This process uses a conventional cobalt/molybdenum hydrodesulfurization catalyst but does not require additional hydrogen. Developed by The Anglo-Iranian Oil Company in 1948. 

RDS Isomax [Residuum desulphurization] A hydrodesulfurization process for removing sulfur compounds from petroleum residues, while converting the residues to fuel oil. Developed by Chevron Research Company in the early 1970s. Ten units were operating in 1988. See also VGO Isomax, VRDS Isomax. 

Trickle-bed reactors are used in catalytic hydrotreating (reaction with H2) of petroleum fractions to remove sulfur (hydrodesulfurization), nitrogen (hydrodenitrogena-tion), and metals (hydrodemetallization), as well as in catalytic hydrocracking of petroleum fractions, and other catalytic hydrogenation and oxidation processes. An example of the first is the reaction in which a sulfur compound is represented by diben-zothiophene (Ring and Missen, 1989), and a molybdate catalyst, based, for example, on cobalt molybdate, is used ... 

One of the major challenges in the petroleum industry today is the removal of sulfur compounds, especially refractive ones such as 4,6-dimethyldibenzo-thiophene (DMDBT), from petroleum fractions such as diesel to concentrations <5-10 ppm from the current values of 50-500 ppm. The current technology is hydrodesulfurization catalyzed by cobalt-nickel-molybdenum sulfides at high pressures. Reducing sulfur concentratios in diesel fuels below 5-10 ppm... 

The replacement of conventional catalytic processes for purification of mixtures by processes involving extraction with ionic liquids has also been envisioned. For example, the extractive removal of sulfur compounds from fuels has shown promising leads for high selectivity for aromatic sulfur compounds, and removal of such compounds has been a major challenge in conventional heterogeneous hydrodesulfurization catalysis (27,296). 

Present State of the Art and Future Challenges in the Hydrodesulfurization of Polyaromatic Sulfur Compounds... 

T-606 Specially compounded refractory oxide support G-39 A cobalt-molybdenum catalyst, used for simultaneous hydrodesulfurization of sulfur compounds and hydrogenation of olefins... 

Natural gas feedstock enters the fuel processing subsystem at about 63 psig (4,5 atm). The fuel is first processed in hydrodesulfurizing unit (HDS) and zinc-oxide (ZnO) beds lo remove any sulfur compounds. The desulfurized fuel is mixed with process steam and preheated to about 850°F (454cC) before entering the reformer, which consists of reactor tubes containing a... 

The basic reactions of the MRG process consist of three stages (1) hydrodesulfurization of sulfur compounds in the hydrocarbon feedstock (2) low-temperature steam reforming (gasification) of desulfurized hydrocarbons and (3) methanation reaction between hydrogen and carbon dioxide in methane gas available by gassification. 

The positive identification of the sulfur compounds in crude oils is a difficult problem often complicated by the lack of reference compounds. This difficulty has been overcome by hydrodesulfurization (see Section VIII), which converts the sulfur compounds into known hydrocarbons. Treatment of a petroleum oil fraction with calcium hexammine converts the benzo[6]thiophenes present into aryl mercaptans, which are readily separable from accompanying aromatic hydrocarbons (e.g., naphthalene) and then identified by hydro-... 

The rates of hydrodesulfurization of benzo[6]thiophene 770,771 and its 3-methyl derivative 772 have been compared with those of other sulfur compounds using hydrogen and a C0O3-M0O3-AI2O3 catalyst. 

The equilibrium constant does, however, decrease with increasing temperature for each particular reaction but still does retain a substantially positive value at 425°C (795°F) which is approaching the maximum temperature at which many of the hydrodesulfurization (especially nondestructive) reactions would be attempted. The data also indicate that the decomposition of sulfur compounds to yield unsaturated hydrocarbons and hydrogen sulfide is not thermodynamically favored at temperatures below 325°C (615°F) and such a reaction has no guarantee of completion until temperatures of about 625°C (1155°F) are reached. However, substantial decomposition of thiols can occur at temperatures below 300°C (570°F) in fact (with only few exceptions), the decomposition of all saturated... 

Nevertheless, the development of general kinetic data for the hydrodesulfurization of different feedstocks is complicated by the presence of a large number of sulfur compounds each of which may react at a different rate because of structural differences as well as differences in molecular weight. This may be reflected in the appearance of a complicated kinetic picture for hydrodesulfurization in which the kinetics is not, apparently, first order (Scott and Bridge, 1971). The overall desulfurization reaction may be satisfied by a second-order kinetic expression when it can, in fact, also be considered as two competing first-order reactions. These reactions are (1) the removal of nonasphaltene sulfur and (2) the removal of asphaltene sulfur. It is the sum of these reactions that gives the second-order kinetic relationship. 

Thus, it has become possible to define certain general trends that occur in the hydrodesulfurization of petroleum feedstocks. One of the more noticeable facets of the hydrodesulfurization process is that the rate of reaction declines markedly with the molecular weight of the feedstock (Figure 4-6) (Scott and Bridge, 1971). For example, examination of the thiophene portion of a (narrowboiling) feedstock and the resulting desulfurized product provides excellent evidence that benzothiophenes are removed in preference to the dibenzothiophenes and other condensed thiophenes. The sulfur compounds in heavy oils and residua are presumed to react (preferentially) in a similar manner. 

It is also generally accepted that the simpler sulfur compounds (e.g., thiols, R-SH, and sulfides, R-S-R1) are (unless steric influences offer resistance to the hydrodesulfurization) easier to remove from petroleum feedstocks than the more complex cyclic sulfur compounds such as the benzothiophenes). It should be noted here that, because of the nature of the reaction, steric influences would be anticipated to play a lesser role in the hydrocracking process. 

Under the usual commercial hydrodesulfurization conditions (elevated temperatures and pressures, high hydrogen-to-feedstock ratios, and the presence of a catalyst), the various reactions that result in the removal of sulfur from the organic feedstock (Table 4-3) occur. Thus, thiols as well as open chain and cyclic sulfides are converted to saturated and/or aromatic compounds depending, of course, on the nature of the particular sulfur compound involved. Benzothio-phenes are converted to alkyl aromatics, while dibenzothiophenes are usually converted to biphenyl derivatives. In fact, the major reactions that occur as part of the hydrodesulfurization process involve carbon-sulfur bond rupture and saturation of the reactive fragments (as well as saturation of olefins). 

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