Operation isobutane alkylation

For example, if a refiner s isobutane costs 25c/ gal, the case is made for Dimersol operation (over alkylation) for any value of propylene up to 25.7c/ gal. 

An afterglow microwave plasma with stabilized pulse power was applied to the activation of zeolite catalysts for isobutane alkylation with butenes. It was found that the pretreatment of zeolite catalysts in a microwave plasma discharge affected their properties. The catalysts exhibited higher activity, stability in operation, and selectivity (the fraction of trimethylpentanes in the alkylate increased). The properties of catalysts after plasma activation depend on the treatment conditions such as plasma temperature and nonequilibrium character and depend only slightly on the initial activity of catalysts, which is primarily controlled by the catalyst preparation conditions. 

Olefins react immediately upon contacting acid. If the acid is cold and saturated with isobutane, alkylation operating problems will be minimized. 

Isomerization. Isomerization of any of the butylene isomers to increase supply of another isomer is not practiced commercially. However, their isomerization has been studied extensively because formation and isomerization accompany many refinery processes maximization of 2-butene content maximizes octane number when isobutane is alkylated with butene streams using HF as catalyst and isomerization of high concentrations of 1-butene to 2-butene in mixtures with isobutylene could simplify subsequent separations (22). One plant (Phillips) is now being operated for this latter purpose (23,24). The general topic of isomerization has been covered in detail (25—27). Isomer distribution at thermodynamic equiUbrium in the range 300—1000 Kis summarized in Table 4 (25). 

Seasonal chances in gasoline sales and heating oil sales compel some modifications to be made in conversion level. Therefore, the conversion pattern of a given catalytic cracking unit can vary from season to season. In summer operations, for instance, higher yields of motor gasoline are desired, both from direct production of 5/430° FVT catalytic naphtha and also from conversion of butylenes and isobutane to alkylate. 

Flowever, information concerning the characteristics of these systems under the conditions of a continuous process is still very limited. From a practical point of view, the concept of ionic liquid multiphasic catalysis can be applicable only if the resultant catalytic lifetimes and the elution losses of catalytic components into the organic or extractant layer containing products are within commercially acceptable ranges. To illustrate these points, two examples of applications mn on continuous pilot operation are described (i) biphasic dimerization of olefins catalyzed by nickel complexes in chloroaluminates, and (ii) biphasic alkylation of aromatic hydrocarbons with olefins and light olefin alkylation with isobutane, catalyzed by acidic chloroaluminates. 

Stratco A process for making a high-octane gasoline component by alkylation of C3 - C5 hydrocarbons with isobutane, catalyzed by sulfuric acid. The product is known as an alkylate. Operated in several oil refineries in the United States. 

This contribution is an in-depth review of chemical and technological aspects of the alkylation of isobutane with lightalkenes, focused on the mechanisms operative with both liquid and solid acid catalysts. The differences in importance of the individual mechanistic steps are discussed in terms of the physical-chemical properties of specific catalysts. The impact of important process parameters on alkylation performance is deduced from the mechanism. The established industrial processes based on the application of liquid acids and recent process developments involving solid acid catalysts are described briefly. 2004 Elsevier Inc. 

Table I gives the compositions of alkylates produced with various acidic catalysts. The product distribution is similar for a variety of acidic catalysts, both solid and liquid, and over a wide range of process conditions. Typically, alkylate is a mixture of methyl-branched alkanes with a high content of isooctanes. Almost all the compounds have tertiary carbon atoms only very few have quaternary carbon atoms or are non-branched. Alkylate contains not only the primary products, trimethylpentanes, but also dimethylhexanes, sometimes methylheptanes, and a considerable amount of isopentane, isohexanes, isoheptanes and hydrocarbons with nine or more carbon atoms. The complexity of the product illustrates that no simple and straightforward single-step mechanism is operative rather, the reaction involves a set of parallel and consecutive reaction steps, with the importance of the individual steps differing markedly from one catalyst to another. To arrive at this complex product distribution from two simple molecules such as isobutane and butene, reaction steps such as isomerization, oligomerization, (3-scission, and hydride transfer have to be involved.

The general treatment of the hydrocarbon stream leaving the alkylation reactor is similar in all processes. First, the acid and hydrocarbon phases have to be separated in a settler. The hydrocarbon stream is fractionated in one or more columns to separate the alkylate from recycle isobutane as well as from propane, n-butane, and (sometimes) isopentane. Because HF processes operate at higher isobutane/alkene ratios than H2S04 processes, they require larger separation units. All hydrocarbon streams have to be treated to remove impurity acids and esters. 

The catalyst can be treated with a solvent to extract hydrocarbon deposits. The most straightforward solvent to use is isobutane, which has been shown to restore catalytic activity only partially. Supercritical solvents have been tested, but they also lead to only partial restoration of the activity. Supercritical alkylation to remove the deposits in situ has been shown in Section III.D.l to be less effective. It is unlikely that this method of operation will lead to a competitive process. 

The catalyst is reported to be a true solid acid without halogen ion addition. In the patent describing the process (239), a Pt/USY zeolite with an alumina binder is employed. It was claimed that the catalyst is rather insensitive to feed impurities and feedstock composition, so that feed pretreatment can be less stringent than in conventional liquid acid-catalyzed processes. The process is operated at temperatures of 323-363 K, so that the cooling requirements are less than those of lower temperature processes. The molar isobutane/alkene feed ratio is kept between 8 and 10. Alkene space velocities are not reported. Akzo claims that the alkylate quality is identical to or higher than that attained with the liquid acid-catalyzed processes. 

Moreover, the efficiency of these catalysts could be modihed by tailoring the nature of the metal oxide support and/or reaction conditions (especially the reaction temperature). In this way, interesting conclusions can be obtained when comparing the isobutane/2-butene alkylation catalyzed on two of the most studied catalysts, that is, beta zeolite and sulfated zirconia, when operating at different reaction temperatures. (Table 13.2). ... 

A, Find the optimum liquid concentration of the propane isobutane mixture in an auto lefrigerated alkylation reactor. The exothermic heat (10 Btu/h) of the alkylation reaction is removed by vaporization of the liquid in the reactor. The vapor is com pressed, condensed, and flashed back into the reactor through a pressure letdown valve. The reactor must operate at 50°F, and the compressed vapors must be condensed at 110°F. 

The use of acidic chloroaluminates as alternative liquid acid catalysts for the alkylation of light olefins with isobutane, for the production of high octane number gasoline blending components, is also a challenge. This reaction has been performed in a continuous flow pilot plant operation at IFP [44] in a reactor vessel similar to that used for dimerization. The feed, a mixture of olefin and isobutane, is pumped continuously into the well stirred reactor containing the ionic liquid catalyst. In the case of ethene, which is less reactive than butene, [pyridinium]Cl/AlCl3 (1 2 molar ratio) ionic liquid proved to be the best candidate (Table 5.3-4). 

Temperature is an important variable in the alkylation process. When alkylating isobutane with butenes, a reaction temperature of 40° to 50° F. produces the highest quality alkylate with the lowest catalyst consumption. Commercial operation has been... 

The catalyst consumption for sulfuric acid alkylation is expressed in terms of pounds of fresh acid depleted per barrel of alkylate produced. When alkylating isobutane with butenes at 50° F. and maintaining an isobutane-olefin ratio of 5 to 1, the acid consumption will average 35 to 40 pounds per barrel when charging 98% acid and discarding 88% acid in a batchwise operation. 

As in sulfuric acid alkylation, the important reaction operating variables are isobutane concentration, catalyst purity, acid-hydrocarbon ratio, and reaction temperature. Normally these variables are maintained at the same level as in sulfuric acid alkylation except for temperature. Most commercial plants operate from 75° to 100° F. This higher operating temperature often allows cooling water rather than the usual vaporizing refrigerants to be used. 

Although the preceding discussion of the sulfuric and hydrofluoric acid processes has been confined to butene alkylation, isobutane has also been alkylated commercially with other olefins. Ethylene, propylene, pentenes, and dimers of butenes have been used for this purpose. It is also possible to use these olefins for the alkylation of isopentane. Such an operation, however, has not achieved commercial acceptance because it produces an inferior alkylate with a high catalyst consumption, and because isopentane is a satisfactory aviation gasoline component in its own right. 

For purposes of plant design and for optimum operation consistent with feed stock availability, it is necessary to be able to predict accurately the octanes of the alkylate produced under varying operating conditions. Such a correlation developed from several hundred pilot plant and commercial plant tests is presented in Figures 7, 8, and 9. This correlation is applicable to sulfuric acid alkylation of isobutane with the indicated olefins, and was developed specifically for the impeller-type reaction system, although it also appears to be satisfactory for use with some other types of reactors. 

Another factor which contributes most to the high cost of the alkylation process is the necessity of having a large excess of isobutane in the reaction zone. This requirement results in increased capital costs for over-sized reactors, settlers, fractionators, and accessories, as well as in increased operating costs of this equipment. Process developments which would allow satisfactory operations at considerably lower isobutane-to-olefin ratios would help reduce these costs. Such developments might again involve improvements in reactors or in catalysts. 

In reviewing the literature one becomes aware that about 12 years ago the petroleum industry was undergoing partial transition into a synthetic chemicals industry and this is reflected in the variety of analyses required. Production of synthetic rubber, 1,3-buta-diene, isobutene, isobutane, styrene, diisobutene, alkylate, iso-octane, copolymer, cumene, and toluene was greatly aided by instrumental analysis including ultraviolet, infrared, mass and emission spectrometry. Without these methods many of the analyses would be entirely impractical because of tediousness, long elapsed time for results, and general expense of operation. 

Isomerization of straight-chain to branched alkanes also increases the octane number, as do alkylates produced by alkene-isoalkane alkylation (such as that of isobutane and propylene, isobutylene, etc.). These large-scale processes are by now an integral part of the petroleum industry. Refining and processing of transportation fuels became probably the largest-scale industrial operation. 

In the ethane-ethylene reaction in a flow system with short contact time, exclusive formation of n-butane takes place (longer exposure to the acid could result in isomerization). This indicates that a mechanism involving a trivalent butyl cation depicted in Eqs. (5.1)—(5.5) for conventional acid-catalyzed alkylations cannot be operative here. If a trivalent butyl cation were involved, the product would have included, if not exclusively, isobutane, since the 1- and 2-butyl cations would preferentially isomerize to the rm-butyl cation and thus yield isobutane [Eq. (5.9)]. It also follows that the mechanism cannot involve addition of ethyl cation to ethylene. Ethylene gives the ethyl cation on protonation, but because it is depleted in the excess superacid, no excess ethylene is available and the ethyl cation will consequently attack ethane via a pentacoordinated (three-center, two-electron) carbocation [Eq. (5.10)] ... 

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