Catalytic gasoline reforming

G. Proticlovasic, N. Jambrec, D. Deursiftar and M. V. Prostenik Determination of catalytic reformed gasoline octane number by high-resolution gas-chromatography. Fuel 69(4), 525-528 (1990). 

The ever increasing demand for higher octane numbers has led to the thermal reforming of already catalytically reformed gasoline. When reforming 84 to 89 Research octane catalirtic reformates, yields of 75 to 93 per cent of 93 to 100 octane finished gasoline are produced. 

Commercially, xylene is obtained by the catalytic reforming of naphthenes in the presence of hydrogen see toluene) or was formerly obtained from coal tar. The material so-produced is suitable for use as a solvent or gasoline ingredient, these uses accounting for a large part of xylene consumption. If xylene is required as a chemical, separation into the iso-... 

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). 

A key process in the production of gasoline, catalytic reforming is used to increase the octane number of light crude fractions having high paraffin and naphthene contents (C7-C8-C9) by converting them to aromatics. 

The main feedstock for catalytic reforming is heavy gasoline (80 to 180°C) available from primary distillation. If necessary, reforming also converts byproduct gasoline from processes such as visbreaking, coking, hydroconversion and heart cuts from catalytic cracking. 

Catalytic cracking is a key refining process along with catalytic reforming and alkylation for the production of gasoline. Operating at low pressure and in the gas phase, it uses the catalyst as a solid heat transfer medium. The reaction temperature is 500-540°C and residence time is on the order of one second. 

The conversion products, other than gas and hydrogen sulfide (H2S), are essentially a gasoline fraction that, after pretreatment, will be converted by catalytic reforming an average quality distillate fraction to be sent to the gas oil pool and an atmospheric residue or vacuum distillate and vacuum residue whose properties and impurity levels (S, N, Conr. 

Furthermore, the major problem of reducing aromatics is focused around gasoline production. Catalytic reforming could decrease in capacity and severity. Catalytic cracking will have to be oriented towards light olefins production. Etherification, alkylation and oligomerization units will undergo capacity increases. 

Toluene disproportionation (TDP) is a catalytic process in which 2 moles of toluene are converted to 1 mole of xylene and 1 mole of benzene this process is discussed in greater detail herein. Although the mixed xylenes from TDP are generally more cosdy to produce than those from catalytic reformate or pyrolysis gasoline, thek principal advantage is that they are very pure and contain essentially no EB. 

A breakdown of the mixed xylene supply sources in the United States is summarized in Table 1 (1). As shown in Table 1, the primary source of xylenes in the United States is catalytic reformate. In 1992, over 90% of the isolated xylenes in the United States were derived from this source. Approximately 9% of the recovered xylenes is produced via toluene disproportionation (TDP). In the United States, only negligible amounts of the xylenes are recovered from pyrolysis gasoline and coke oven light oil. In other parts of the world, pyrolysis gasoline is a more important source of xylenes. 

The majority of xylenes, which are mostly produced by catalytic reforming or petroleum fractions, ate used in motor gasoline (see Gasoline and other MOTORFUELs). The majority of the xylenes that are recovered for petrochemicals use are used to produce PX and OX. PX is the most important commercial isomer. Almost all of the PX is converted to terephthaUc acid and dimethylterephthalate, and then to poly(ethylene terephthalate) for ultimate use in fibers, films, and resins. 

Mixtures of CO—H2 produced from hydrocarbons, as shown in the first two of these reactions, ate called synthesis gas. Synthesis gas is a commercial intermediate from which a wide variety of chemicals are produced. A principal, and frequendy the only source of hydrogen used in refineries is a by-product of the catalytic reforming process for making octane-contributing components for gasoline (see Gasoline and OTHER MOTOR fuels), eg. 

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

Toluene, Benzene, and BTX Reeoveiy. The composition of aromatics centers on the C - and Cg-fraction, depending somewhat on the boihng range of the feedstock used. Most catalytic reformate is used directiy in gasoline. That part which is converted to benzene, toluene, and xylenes for commercial sale is separated from the unreacted paraffins and cycloparaffins or naphthenes by hquid—hquid extraction or by extractive distillation. It is impossible to separate commercial purity aromatic products from reformates by distillation only because of the presence of azeotropes, although comphcated further by the closeness in boihng points of the aromatics, t/o-paraffin, and unreacted C -, C -, and Cg-paraffins. 

Automotive Fuels. About 90% of the toluene generated by catalytic reforming is blended into gasoline as a component of >C5 reformate. 

The main producers of benzene in Canada are the Nova Corp. of Alberta, Petro-Canada, Inc., and Shell Canada Ltd. These three companies have an armual capacity of 567,000 t. Most Canadian benzene is obtained from catalytic reformate, pyrolysis gasoline, and hydrodealkylation. Coal is not an important source of benzene in Canada. 

Some of the principal Japanese producers of benzene are Mitsubishi Petrochemical Co., Ltd., Nippon Steel Chemical Co., Ltd., Sanyo Petrochemical Ltd., and Idemitsu Kosan Ltd. Until 1967, the main source of Japanese benzene was coal-based. Today, approximately 40—45% of benzene production in Japan is based on pyrolysis gasoline (74), about 40% catalytic reformate, and the remainder coke oven light oil and thermal hydrodealkylation. 

---