Isopentane alkylation

Comparing the product selectivity at low conversion in the hydrogenolysis of 2,2-dimethylbutane for the two catalysts is noteworthy. Zirconium hydride supported on siUca does not produce neopentane, but only isopentane (10%) as a Cs product in agreement with a /1-alkyl transfer as a key step for the carbon-carbon cleavage (no neopentane can be formed through this mechanism, Scheme 25). 

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.

Theoretically, even the direct alkylation of carbenium ions with isobutane is feasible. The reaction of isobutane with a r-butyl cation would lead to 2,2,3,3-tetramethylbutane as the primary product. With liquid superacids under controlled conditions, this has been observed (52), but under typical alkylation conditions 2,2,3,3-TMB is not produced. Kazansky et al. (26,27) proposed the direct alkylation of isopentane with propene in a two-step alkylation process. In this process, the alkene first forms the ester, which in the second step reacts with the isoalkane. Isopentane was found to add directly to the isopropyl ester via intermediate formation of (non-classical) carbonium ions. In this way, the carbenium ions are freed as the corresponding alkanes without hydride transfer (see Section II.D). This conclusion was inferred from the virtual absence of propane in the product mixture. Whether this reaction path is of significance in conventional alkylation processes is unclear at present. HF produces substantial amounts of propane in isobutane/propene alkylation. The lack of 2,2,4-TMP in the product, which is formed in almost all alkylates regardless of the feed (55), implies that the mechanism in the two-step alkylation process is different from that of conventional alkylation. 

With propene, n-butene, and n-pentene, the alkanes formed are propane, n-butane, and n-pentane (plus isopentane), respectively. The production of considerable amounts of light -alkanes is a disadvantage of this reaction route. Furthermore, the yield of the desired alkylate is reduced relative to isobutane and alkene consumption (8). For example, propene alkylation with HF can give more than 15 vol% yield of propane (21). Aluminum chloride-ether complexes also catalyze self-alkylation. However, when acidity is moderated with metal chlorides, the self-alkylation activity is drastically reduced. Intuitively, the formation of isobutylene via proton transfer from an isobutyl cation should be more pronounced at a weaker acidity, but the opposite has been found (92). Other properties besides acidity may contribute to the self-alkylation activity. Earlier publications concerned with zeolites claimed this mechanism to be a source of hydrogen for saturating cracking products or dimerization products (69,93). However, as shown in reaction (10), only the feed alkene will be saturated, and dehydrogenation does not take place. 

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. 

In 1989, the NDF Company opened a facility in Georgetown, South Carolina to produce low density polyethylene. Manufacturing of the polyethylene is done in two 50-ton reactors that are encased individually within their own 8-story-high process unit. The main raw materials for the manufacturing operations include ethylene, hexane, and hutene. The polymerization is completed in the presence of a catalyst. The hase chemicals for the catalyst are aluminum alkyl and isopentane. The reactor and catalyst preparation areas are on a distributed control system (DCS). A simplihed process flow diagram is attached. 

In the catalyst preparation area where the fire occurred, aluminum alkyl and isopentane are mixed in a batch blending operation in three 8000-gallon kettles. The flow rates of components are regulated by an operator at the control room. Temperature, pressure, and liquid level within the kettles are monitored by the control room operator. The formulated catalyst is stored in four 12,000-gallon vertical storage tanks within this process unit. Aluminum alkyl is a pyrophoric material and isopentane is extremely flammable. Each vessel was insulated and equipped with a relief valve sized for external fire. 

The isopentane for the catalyst preparation unit is stored as a liquid in a 60-ton horizontal (bullet) storage tank. The aluminum alkyls and other required chemicals for this process are received in small truck trailers and kept beneath a metal canopy. 

The catalyst preparation area is positioned between the two polyethylene production units with 60 feet separating each one. The aluminum alkyls storage canopy and isopentane horizontal storage tank are located at a remote area at an approximate distance of 250 feet away from the production and utility areas. The isopentane is transported to the catalyst preparation area through a 3-inch pipeline. A remote actuated isolation valve on this supply line that fails closed is located at the isopentane storage tank. This control valve and an associated isopentane feed pump are managed by the operator in the control room. 

In fact, the C-H bond activation by the zirconium or tantalum hydride on 2,2-dimethylbutane can occur in three different positions (Scheme 3.5) from which only isobutane and isopentane can be obtained via a P-alkyl transfer process the formation of neopentane from these various metal-alkyl structures necessarily requires a one-carbon-atom transfer process like an a-alkyl transfer or carbene deinsertion. This one-carbon-atom process does not preclude the formation of isopentane but neopentane is largely preferred in the case of tantalum hydride. 

Butane isomerization and pentane-hexane isomerization are the two most important isomerization processes. Isobutane is utilized primarily as alkylate feedstock. Isopentanes and isohexanes have become valuable high-octane blending components in gasoline. 

This alkyl halide will also yield isopentane. 

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. 

Pentane isomerization was carried out on a much smaller scale. Isopentane, because of its high octane number and good lead response, was blended directly into aviation gasoline. It also served to increase the volatility of blends containing such high-boiling components as alkylate. 

Isopentane and trimethylpentanes (C8 alkanes) are inevitably formed whenever isobutane is alkylated with any alkene. They are often called abnormal products. Formation of isopentane involves the reaction of a primary alkylation product (or its carbocation precursor, e.g., 3) with isobutane. The cation thus formed undergoes alkyl and methyl migration and, eventually, P scission ... 

Superacids were shown to have the ability to effect the protolytic ionization of a bonds to form carbocations even in the presence of benzene.190 The formed car-bocations then alkylate benzene to form alkylbenzenes. The alkylation reaction of benzene with Ci—C5 alkanes (methane, ethane, propane, butane, isobutane, isopentane) are accompanied by the usual acid-catalyzed side reactions (isomerization, disproportionation). Oxidative removal of hydrogen by SbF5 is the driving force of the reaction ... 

Isomerization—A refining process which alters the fundamental arrangement of atoms in the molecule, Used to convert normal butane into isobutane, as alkylation process feedstock, and normal pentane and hexane into isopentane and isohexane, high-octane gasoline components,... 

Similar reactions were observed with the CH3CH2F-SbF5 complex (Scheme 5.19). When the complex was treated with isobutane or isopentane, direct alkylation products were observed [Eq. (5.59)]. 

Propane as a degradation product of polyethylene (a byproduct in the reaction) was ruled out because ethylene alone under the same conditions does not give any propane. Under similar conditions but under hydrogen pressure, polyethylene reacts quantitatively to form C3 to C6 alkanes, 85% of which are isobutane and isopentane. These results further substantiate the direct alkane alkylation reaction and the intermediacy of the pentacoordinate carbonium ion. Siskin also found that when ethylene was allowed to react with ethane in a flow system, n-butane was obtained as the sole product, indicating that the ethyl cation is alkylating the primary C—H bond through a five-coordinate carbonium ion [Eq. (5.66)]. 

Corma and co-workers152 have performed a detailed theoretical study (B3PW91/6-31G level) of the mechanism of the reactions between carbenium ions and alkanes (ethyl cation with ethane and propane and isopropyl cation with ethane, propane, and isopentane) including complete geometry optimization and characterization of the reactants, products, reaction intermediates, and transition states involved. Reaction enthalpies and activation energies for the various elemental steps and the equilibrium constants and reaction rate constants were also calculated. It was concluded that the interaction of a carbenium ion and an alkane always results in the formation of a carbonium cation, which is the intermediate not only in alkylation but also in other hydrocarbon transformations (hydride transfer, disproportionation, dehydrogenation). 

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