Benzene is considered to be environmentally hazardous. As a result, the State of California and the United States Environmental Protection Agency have instituted regulations to limit the amount of benzene which may be present in gasoline. As of January 2011, the US MSAT-2 (Mobile Source Air Toxics) regulation requires reduction of this annual average benzene content in gasoline to no greater than 0.62 volume %.
One known route for reducing the benzene content of gasoline is to selectively alkylate the benzene using a lower olefin. For example, Holtermann et al U.S. Pat. No. 5,149,894 describes a process for converting benzene to alkylated benzenes in a gasoline blend stock. The process involves contacting a benzene-containing gasoline blend stock with a C2 to C4 olefin stream in the presence of a catalyst containing the zeolite, SSZ-25, to produce an alkylated light hydrocarbon stream with reduced benzene content.
Cheng et al. U.S. Pat. No. 5,545,788 describes a process for the production of a more environmentally suitable gasoline by removing a substantial portion of the benzene in gasoline by alkylation of reformate. The process involves alkylation using a light olefin feed at low temperature over the zeolite catalyst, MCM-49.
Umansky el al. U.S. Pat. No. 7,476,774 describes a process where light olefins including ethylene and propylene are extracted from refinery off-gases, such as from a catalytic cracking unit, into a light aromatic stream, such as a reformate containing benzene and other single ring aromatic compounds, which is then reacted with the light olefins to form a gasoline boiling range product containing alkylaromatics. The alkylation reaction is carried out in the liquid phase with a catalyst which preferably comprises a member of the MWW family of zeolites, such as MCM-22, using a fixed catalyst bed.
However, in addition to limiting the benzene level in gasoline, current and ongoing regulations restrict the content of residue, which consists of heavy hydrocarbon components with boiling points outside the gasoline boiling range. The US standard specification for automotive spark-ignition engine fuel (ASTM D4814) requires that the residue (heavies) in the gasoline product is no more than 2 volume %. Moreover, some refiners have low gasoline endpoint requirements such that, at high benzene conversion during reformate alkylation, the alkylation product may not be fully blendable into the gasoline pool at these refineries. This is believed to be at least partially due to the presence in the reformate feed of C4 and heavier olefins, such as C4-C8 olefins, which, during alkylation, can react with the benzene in the reformate in addition to the added light olefins to produce non-blendable C14 and heavier components.
According to the present invention, it has now been found that the undesirable formation of heavy components in the alkylation of a benzene-containing refinery gasoline stream, such as a reformate fraction or light naphtha, with an olefin alkylating agent can be reduced by initially reacting the C4 and heavier olefins in the gasoline stream with part of the benzene component of the gasoline stream to produce a C10+ product. This C10+ product can then be removed, for example by distillation, before the remainder of the gasoline stream is supplied to an alkylation unit for reaction with added light olefins to further reduce the benzene content of the gasoline.
USPTO Backgrounds
USPTO Backgrounds