Gasoline fractions/catalytic processes

A catalytic reforming process produces similar products. The relative amounts may differ, however, depending on the catalyst selectivity and process conditions, the main product, of course, is a high octane C, -1- gasoline fraction. 

RCH [Ruhrchemie] A process for increasing the octane rating of gasolines by catalytic isomerization of the olefin fraction, the double bonds migrating from the terminal positions. Developed by Ruhr Chemie in the 1940s. 

Crude oil typically contains little to no olefinic compounds. Through refining and processing, however, olefins are produced and become a part of various crude oil fractions. Olefins can be found in thermally cracked and catalytically cracked gasoline fractions as well as in FCC cycle oils and coker gas oils. For this reason, it is not unusual for finished gasoline and distillate blends to contain a high-olefin-content stream. 

Reforming Both thermal and catalytic processes are utilized to convert naphtha fractions into high-octane aromatic compounds. Thermal reforming is utilized to convert heavy naphthas into gasoline-quality aromatics. Catalytic reforming is utilized to convert straight-run naphtha fractions into aromatics. Catalysts utilized include oxides of aluminum, chromium, cobalt, and molybdenum as well as platinum-based catalysts. 

When naphtha or naphthenic gasoline fractions are catalytically reformed, they usually yield a Cx aromatics stream that is comprised of mixed xylenes and ethylbenzene. It is possible to separate the ethylbenzene and o-xylene by fractionation. It is uneconomic to separate the m- and p-xylenes in this manner because of the closeness of their boiling points. To accomplish the separation, a Werner-type complex for selective absoiption of p-xylene from the feed mixture may be used. Or, because of the widely different freezing points of the two xylene isomers, a process of fractional crystallization may be used. To boost the p-xylene yield, die filtrate from the crystallization step can be catalytically isomerized. 

Other catalytic reactions carried out in fluidized-bed reactors are the oxidation of naphthalene to phthalic anhydride [2, 6, 80] the ammoxidation of isobutane to mcthacrylonitrilc [2] the synthesis of maleic anhydride from the naphtha cracker C4 fraction (Mitsubishi process [81, 82]) or from n-butane (ALMA process [83], [84]) the reaction of acetylene with acetic acid to vinyl acetate [2] the oxychlorination of ethylene to 1,2-di-chloroethane [2, 6, 85, 86] the chlorination of methane [2], the reaction of phenol with methanol to cresol and 2,6-xylenol [2, 87] the reaction of methanol to gasoline... 

The high influence of cracking catalyst on PE conversion was confirmed by Aguado et al. [11] in a continuous screw kiln reactor. The application of a sophisticated laboratory Al-MCM-41 cracking catalyst and process temperature of 400-450°C led to 85-87% yield of gas and gasoline fractions (C1-C12). Besides olefins and n- and iso-paraffins some quantity of aromatics, 5 wt% was determined in the process products. In the same reactor system with a noncatalytic process the gas yield was halved while similarly as in case of the fluid reactor system yields of gas oil and heavy waxes fraction (C13-C55) attained values of 62% (compared with 4 wt% in catalytic process) [12]. 

In the first group, the production of aromatics is a complementary objective to the refinery processing of gasoline fractions to raise the aromatic content, which evidently links these refining functions. Catalytic reforming processes are used to convert paraffins to naphthenes (cycloparaffins) to be followed by dehydrogenation of naphthenes to aromatics (Chap. 18). Since aromatization of naphthenes is an easier process to accomplish than cycloalkylation, the emphasis in refinery operations is on maximization of the second step in this sequence, when there is an adequate supply of naphthenes. The demand for the aromatics component of gasoline will compete with the feedstock aromatic need from this source. 

Other industrial processes that have taken advantage of the process intensification deriving from the introduction of reactive (catalytic) distillation are (i) production of high purity isobutene, for aromatic alkylation (ii) production of isopropyl alcohol by hydration of propylene (iii) selective production of ethylene glycol, which involves a great number of competitive reactions and (iv) selective desulfurization of fluid catalytic cracker gasoline fractions as well as various selective hydrogenations. Extraction distillation is also used for the production of anhydrous ethanol. 

Isomerization Catalytic process to improve the octane number of gasoline fractions. Based on isomerization reactions of n-alkanes. 

The maximums of liquid product yields (80 and 52.5 mass% in modes 1 and 2, respectively) were observed at the same dose values of about 6 kGy. However, gasoline fractions produced in the two modes considerably differed in their hydrocarbon contents. At the temperature of 375°C, isoalkane yields were comparable with those observed in the catalytic process at the temperatures above 600°C. The unusually high yields of isoparaffins in the RTC modes characterized by relatively low values of temperature and dose rate were attributed to the effects of energy transfer from paraffin to aromatic components of the hydrocarbon mixture. 

FIGURE 15.13 Hydrocarbon content of gasoline fraction produced by bitumen processing. TCC, thermo-catalytic cracking RTC, radiation-thermal cracking. 

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