Sulfur catalytic

Time will show if there is need for desulfurization of high speed Diesel fuels. There is no doubt that many companies are actively studying desulfurization processes so as to be in a position to make the best choice. Of those for which published information is available for full scale operation, the most attractive seemed to be sulfur dioxide and furfural extraction, the latter having merit because it has successfully handled high sulfur catalytically cracked recycle stocks. The previously mentioned extraction process using anhydrous hydrogen fluoride also seems attractive because of the low treatment and high yield of refined product, but, until the results of commercial operation are fully known its merits cannot be established. 

Since it is difiScuh to obtain diesd soot with constant prop es (the composition dq> ids on the engine load) a model soot was applied (Printex-U, a flame soot kindly provided by Degussa). This soot has a N2-BET surface area of 96 mV and contains approximately 5 wt% of adsorbed hydrocarbons and 0 2-0.4 wt% sulfur. Catalytic soot oxidation temperatures were d ermined in a thermobalance (STA 1500H). About 4 mg catalyst, 2 mg soot and 54 mg SiC were applied as a sample. A heating rate of 10 K/min and a flow rate of 50 ml/min 21 vol% O2 in N2 wa"e used. The maximum of the DSC curve was defined as the oxidation temperature. Samples refored to as tight contact were intensively milled in a ball mill for one hour, before dilution with SiC and thermal analysis, whereas loose contact was established by simply mixing of the catalyst and soot with a spatula. 

Most platinum metal catalysts (with the exception of Adams catalyst) are stable and can be kept for many years without appreciable loss of activity, but they can be deactivated by many substances, particularly by compounds of divalent sulfur. Catalytic activity is sometimes increased by addition of small amounts of platinum or palladium salts or mineral acid. The increase in the activity may simply be the result of neutralization of alkaline impurities in the catalyst. 

Catalytic gas-phase reactions play an important role in many bulk chemical processes, such as in the production of methanol, ammonia, sulfuric acid, and nitric acid. In most processes, the effective area of the catalyst is critically important. Since these reactions take place at surfaces through processes of adsorption and desorption, any alteration of surface area naturally causes a change in the rate of reaction. Industrial catalysts are usually supported on porous materials, since this results in a much larger active area per unit of reactor volume. 

The gas oil cut from catalytic cracking called Light Cycle Oil (LCO), is characterized by a very low cetane number (about 20), high contents in aromatics, sulfur and nitrogen, all of which strongly limit its addition to the diesel fuel pool to a maximum of 5 to 10%. 

However, such a level can still be considered too high for vehicles having 3-way catalytic converters. In fact, results observed in the United States (Benson et al., 1991) and given in Figure 5.20 show that exhaust pollutant emissions, carbon monoxide, hydrocarbons and nitrogen oxides, increase from 10 to 15% when the sulfur level passes from 50 ppm to about 450 ppm. This is explained by an inhibiting action of sulfur on the catalyst though... 

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

H2S is found with the reservoir gas and dissolved in the crude (< 50 ppm by weight), but it is formed during refining operations such as catalytic cracking, hydrodesulfurization, and thermal cracking or by thermal decomposition of sulfur[Pg.322]

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). 

Feedstocks come mainly from catalytic cracking. The catalyst system is sensitive to contaminants such as dienes and acetylenes or polar compounds such as water, oxygenates, basic nitrogen, organic sulfur, and chlorinated compounds, which usually require upstream treatment. 

Mercaptans are naturally present in crude oil (Chapters 1 and 8), or they result from the decomposition of other sulfur compounds during thermai or catalytic cracking operations. 

A new dimension to acid-base systems has been developed with the use of zeolites. As illustrated in Fig. XVIII-21, the alumino-silicate faujasite has an open structure of interconnected cavities. By exchanging for alkali metal (or NH4 and then driving off ammonia), acid zeolites can be obtained whose acidity is comparable to that of sulfuric acid and having excellent catalytic properties (see Section XVIII-9D). Using spectral shifts, zeolites can be put on a relative acidity scale [195]. An important added feature is that the size of the channels and cavities, which can be controlled, gives selectivity in that only... 

Catalytic hydrogenation is mostly used to convert C—C triple bonds into C C double bonds and alkenes into alkanes or to replace allylic or benzylic hetero atoms by hydrogen (H. Kropf, 1980). Simple theory postulates cis- or syn-addition of hydrogen to the C—C triple or double bond with heterogeneous (R. L. Augustine, 1965, 1968, 1976 P. N. Rylander, 1979) and homogeneous (A. J. Birch, 1976) catalysts. Sulfur functions can be removed with reducing metals, e. g. with Raney nickel (G. R. Pettit, 1962 A). Heteroaromatic systems may be reduced with the aid of ruthenium on carbon. 

Nearly all commercial acetylations are realized using acid catalysts. Catalytic acetylation of alcohols can be carried out using mineral acids, eg, perchloric acid [7601-90-3], phosphoric acid [7664-38-2], sulfuric acid [7664-93-9], benzenesulfonic acid [98-11-3], or methanesulfonic acid [75-75-2], as the catalyst. Certain acid-reacting ion-exchange resins may also be used, but these tend to decompose in hot acetic acid. Mordenite [12445-20-4], a decationized Y-zeohte, is a useful acetylation catalyst (28) and aluminum chloride [7446-70-0], catalyzes / -butanol [71-36-3] acetylation (29). 

In the early versions, ethylene cyanohydrin was obtained from ethylene chlorohydrin and sodium cyanide. In later versions, ethylene oxide (from the dkect catalytic oxidation of ethylene) reacted with hydrogen cyanide in the presence of a base catalyst to give ethylene cyanohydrin. This was hydrolyzed and converted to acryhc acid and by-product ammonium acid sulfate by treatment with about 85% sulfuric acid. 

Dehydration or Chemical Theory. In the dehydration or chemical theory, catalytic dehydration of ceUulose occurs. The decomposition path of ceUulose is altered so that flammable tars and gases are reduced and the amount of char is increased ie, upon combustion, ceUulose produces mainly carbon and water, rather than carbon dioxide and water. Because of catalytic dehydration, most fire-resistant cottons decompose at lower temperatures than do untreated cottons, eg, flame-resistant cottons decompose at 275—325°C compared with about 375°C for untreated cotton. Phosphoric acid and sulfuric acid [8014-95-7] are good examples of dehydrating agents that can act as efficient flame retardants (15—17). 

Thiothionyl Fluoride and Difluorodisulfane. Thiothionyl fluoride [1686-09-9] S=SF2, and difluorodisulfane [13709-35-8] FSSF, are isomeric compounds which may be prepared as a mixture by the action of various metal fluorides on sulfur vapor or S2CI2 vapor. Chemically, the two isomers are very similar and extremely reactive. However, in the absence of catalytic agents and other reactive species, FSSF is stable for days at ordinary temperatures and S=SF2 may be heated to 250°C without significant decomposition (127). Physical properties of the two isomers are given in Table 6. The microwave spectmm of S=SF2 has been reported (130). 

Prior to methanation, the gas product from the gasifier must be thoroughly purified, especially from sulfur compounds the precursors of which are widespread throughout coal (23) (see Sulfurremoval and recovery). Moreover, the composition of the gas must be adjusted, if required, to contain three parts hydrogen to one part carbon monoxide to fit the stoichiometry of methane production. This is accompHshed by appHcation of a catalytic water gas shift reaction. 

Properties. Table 4 contains typical gasoline quaUty data from the New Zealand plant (67). MTG gasoline typically contains 60 vol % saturates, ie, paraffins and naphthenes 10 vol % olefins and 30 vol % aromatics. Sulfur and nitrogen levels in the gasoline are virtually lul. The MTG process produces ca 3—7 wt % durene [95-93-2] (1,2,4,5-tetra-methylbenzene) but the level is reduced to ca 2 wt % in the finished gasoline product by hydrodealkylation of the durene in a separate catalytic reactor. 

Reduction of metal oxides with hydrogen is of interest in the metals refining industry (94,95) (see Metallurgy). Hydrogen is also used to reduce sulfites to sulfides in one step in the removal of SO2 pollutants (see Airpollution) (96). Hydrogen reacts directiy with SO2 under catalytic conditions to produce elemental sulfur and H2S (97—98). Under certain conditions, hydrogen reacts with nitric oxide, an atmospheric poUutant and contributor to photochemical smog, to produce N2 ... 

Aniline Oxidation. Even though this is quite an old process, it still has limited use to produce hydroquinone on a commercial scale. In the first step, aniline is oxidized by manganese dioxide in aqueous sulfuric acid. The resulting benzoquinone, isolated by vapor stripping, is reduced in a second step by either an aqueous acidic suspension of iron metal or by catalytic hydrogenation. 

Starting from Benzene. In the direct oxidation of benzene [71-43-2] to phenol, formation of hydroquinone and catechol is observed (64). Ways to favor the formation of dihydroxybenzenes have been explored, hence CuCl in aqueous sulfuric acid medium catalyzes the hydroxylation of benzene to phenol (24%) and hydroquinone (8%) (65). The same effect can also be observed with Cu(II)—Cu(0) as a catalytic system (66). Efforts are now directed toward the use of Pd° on a support and Cu in aqueous acid and in the presence of a reducing agent such as CO, H2, or ethylene (67). Aromatic... 

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