Industrial refinery alkylation

Refinery alkylation takes place at high temperatures and pressures without catalysts. However, all industrially relevant processes proceed at low-temperatures in the presence of highly acidic catalysts. By appropriate choice of operating conditions, most of the alkylate can be made to fall within the gasoline boiling range with RONS of94-99 and MONs of 88-94. 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

As we learned in Chapter 8, the official production of propylene is usually about half that of ethylene, only because a large part of the propylene is used by petroleum refineries internally to alkylate gasolines. This captive use is not reported. Of the propylene used for chemical manufacture, nearly 40% is polymerized to polypropylene, to be discussed in a later chapter. Of the remaining amount of propylene, seven chemicals from the top 50 are manufactured. These are listed in Table 10.1. Their industrial manufacturing methods are summarized in Fig. 10.1. Note that four of these chemicals, cumene, phenol, acetone, and bisphenol A, are also derived from a second basic organic chemical, benzene. 

Studies have been made thruout the refining industry in an effort to utilize selected stocks for the production of jet fuels. Basically, this would amount to determining the stability of many stocks, for example, straight run gasolines, distillates, kerosines, alkylate bottoms, and whatever else is available from refinery streams. Those with best heat stability, by laboratory test, could then be blended into jet fuels meeting required... 

Mixed cresols, also known as cresylic acids, the lowest among the alkyl phenols, were primarily produced as by-products from coal carbonization plants or recovered from the petroleum refinery caustic washes. These cresols obtained from natural sources were known to the chemical industry for the last 75 years and had limited uses. Production of synthetic cresols from toluene opened up new avenues for these products... 

Many industrial processes are based on acid/base catalysis (over 130). Examples include alkylation, etherification, cracking, dehydration, condensation, hydration, oligomerizations, esterification, isomerization and disproportionation. The dimensions of the processes range from very large scale in the field of refinery (thousand tons per day) to very small productions in fine and specialty chemical industries. In the latter case, adds and bases are often used in stoichiometric quantities, leading thus to large amounts of waste. 

Iso-butane is a highly demanded chemical in the refinery industry for the production of alkylates (by alkylation with butenes), and methyl tert-butyl ether (MTBE) (from isobutene and methanol), both important additives for reformulated gasolines. n-Butane isomerization is performed over platinum supported on chlorinated alumina. The chlorine compound which is continuously supplied to the feed in order to maintain the activity [1] is harmful to the environment. 

Akolidine. [Loiiza] Alkyl pyridine mixture ctXTOsion inhibitor for metals, acid pickling, industrial add deaning, oUfield processes and treatment of oil refinery equip. 

The substances detected included herbicides, such as Alachlor, butachlor, atrazine, cyanazine, propazine, and simazine insecticides, such as chlordane, heptachlor, dield-rin, eldrin, and DDE as a DDT metabolite and industrial organics, which included alkylbenzenes such as toluene, xylenes, ethylbenzene alkanes such as decane through pentadecane naphtalene and methylnaphtalenes alkyl phthalates, used as plasticizers chlorinated methanes and ethanes, especially CHCI3 chlorinated benzenes and chlorinates phenols benzaldehyde dicyclopentadiene, etc. Of these compounds, the hydrocarbons are typical of oil refinery operations, and the chlorinated benzenes and phenols are associated with herbicide and insecticide production. 

My own technical experience has pretty much followed this history of distillation simulation. My practical experience started back in a high-school chemistry class in which we performed batch distillations. Next came an exposure to some distillation theory and running a pilot-scale batch distillation column as an undergraduate at Penn State, learning from Arthur Rose and Black Mike Cannon. Then, there were five years of industrial experience in Exxon refineries as a technical service engineer on pipestills, vacuum columns, light-ends units, and alkylation units, all of which used distillation extensively. 

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