Liquid acid catalysts

The use of acidic chloroaluminates as alternative liquid acid catalysts for the allcy-lation 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). 

The technology and chemistry of isoalkane-alkene alkylation have been thoroughly reviewed for both liquid and solid acid catalysts (15) and for solid acid catalysts alone (16). The intention of this review is to provide an up-to-date overview of the alkylation reaction with both liquid and solid acids as catalysts. The focus is on the similarities and differences between the liquid acid catalysts on one hand and solid acid catalysts, especially zeolites, on the other. Thus, the reaction mechanism, the physical properties of the individual catalysts, and their consequences for successful operation are reviewed. The final section is an overview of existing processes and new process developments utilizing solid acids. 

In the case of the butene isomers, the addition will lead to different isooctyl cations, depending on the isomer and the type of carbenium ion. The reactions involving s-butyl ions are likely to be negligible for liquid acid catalysts and of minor importance for zeolites. 

With both liquid acid catalysts, but presumably to a higher degree with sulfuric acid, hydrides are not transferred exclusively to the carbenium ions from isobutane, but also from the conjunct polymers 44,46,71). Sulfuric acid containing 4-6 wt% of conjunct polymers produces a much higher quality alkylate than acids without ASOs (45). Cyclic and unsaturated compounds, which are both present in conjunct polymers, are known to be hydride donors (72). As was mentioned in Section II.B, these species can abstract a hydride from isobutane to form the -butyl cation, and they can give a hydride to a carbenium ion, producing the corresponding alkane, for example the TMPs, as shown in reactions (7) and (8). 

Figure 13.1 Industrial processes carried out on oxides, halides, and liquid acid catalysts (After Ref. 5).

Concentrated sulfuric acid and hydrogen fluoride are still mainly used in commercial isoalkane-alkene alkylation processes.353 Because of the difficulties associated with these liquid acid catalysts (see Section 5.1.1), considerable research efforts are still devoted to find suitable solid acid catalysts for replacement.354-356 Various large-pore zeolites, mainly X and Y, and more recently zeolite Beta were studied in this reaction. Considering the reaction scheme [(Eqs (5.3)—(5.5) and Scheme 5.1)] it is obvious that the large-pore zeolitic structure is a prerequisite, since many of the reaction steps involve bimolecular bulky intermediates. In addition, the fast and easy desorption of highly branched bulky products, such as trimethylpentanes, also requires sufficient and adequate pore size. Experiments showed that even with large-pore zeolite Y, alkylation is severely diffusion limited under liquid-phase conditions.357... 

Fig. 2. Proposed reaction mechanism for methyl N—phenyl carbamate condensation in a liquid acid catalyst (a) and over a sulfonic acid resin(b).

There have been a number of reports of improved selectivity with sulfonic acid resin catalysts compared with conventional liquid acid catalysts[6—9]. Various explanations have also been proposed. If mechanisms usually postulated for condensation reactions with liquid Br0nsted acid [10] and solid acid catalysts [11] are adopted, the sequence of steps shown in Fig. 2 could be considered for the condensation of MFC. Both mechanisms incorporate the essential features of known carbenium ion chemistry, i.t., electrophilic attack on the aromatic ring by polar carbenium ion intermediates. Note that MDU is formed by this attack on the benzene ring of MPC, while the N—benzyl compound by the attack on nitrogen atom. 

Solid acid catalysts such as mixed oxides (chalcides) have been used extensively for many years in the petroleum industry and organic synthesis. Their main advantage compared with liquid acid catalysts is the ease of separation from the reaction mixture, which allows continuous operation, as well as regeneration and reutilization of the catalyst. Furthermore, the heterogeneous solid catalysts can lead to high selectivity or specific activity. Due to the heterogeneity of solid superacids, accurate acidity measurements are difficult to carry out and to interpret. Up until now, the most useful way to estimate the acidity of a solid catalyst is to test its catalytic activity in well-known acid-catalyzed reactions. 

Two reports demonstrate that Bronsted (Olah et al., 1999) or Lewis acids (Oakes et al., 1999) may be more reactive in sc C02 than in organic solvents. The isobutane-isobutylene alkylation (eq. 2.2), which is used commercially to increase the octane numbers in automotive fuels, has been demonstrated to occur in sc C02 with several liquid acid catalysts (Olah et al., 1999). Increased selectivity for Cg-alkylates is observed in sc C02 relative to neat acid media when anhydrous HF, pyridine poly(hydrogen fluoride) (PPHF),... 

In 1999, Akzo Nobel (which later sold its catalyst division to Albemarle) patented a new technology for alkylating hydrocarbons based on a zeolite acid catalyst [193]. This new process, AlkyClean, was then designed by ABB Lummus and Albemarle, and a 10 barrels per stream day (BPSD) demonstration unit came online in Finland in 2002. AlkyClean produces a high-quality sulfur-free alkylate (96 octane), eliminating all the drawbacks of the liquid acid catalyst technologies. There are no add-soluble oil waste streams, the reactor operates at 50-90 °C, and the catalyst is a solid, noncorrosive material, which is easily transported and stored. 

Homogeneous reactions using H2S04 and A1C13 in industrial processes give rise to many problems that must be solved, for instance, corrosion of the reaction vessels or reactors and difficulties in treating the acids after reaction because of environmental problems. In particular, the disposal of liquid acid catalysts such as H2S04 requires expensive treatment to make... 

One of the first commercial-scale catalytic distillation processes was that for the production of methyl acetate [17]. In this esterification process the liquid acid catalyst is continuously added to the reactant mixture it finishes up in the bottoms and, following neutralization, in the wastewater from the plant. 

Schechler, J.C. Schmidt, R.J. Motor fuel alkylation advances beyond liquid acid catalysts. Paper at Annual Meeting of National Petroleum Refiners Association, San Antonio, TX, Paper AM-97-47, Mar 16-18, 1997. 

There are many examples of the application of CD or RD for esterification.f" Esterification of methanol or ethanol with acetic acid forms methyl acetate or ethyl acetate, respectively. Methyl acetate is important in the manufacture of polyesters and is an important solvent for cellulose while ethyl acetate is used in inks, fragrances, and pharmaceuticals. The manufacture of high-purity methyl acetate is difficult because of the equilibrium limitation and also the formation of azeotropes. The production of methyl acetate by Eastman Chemical Co. was the first commercial application of RD using a homogeneous liquid acid catalyst. Only one RD column and two smaller columns for processing sidestreams are required while in the conventional methyl acetate synthesis, two reactors and eight distillation columns are required. 

As mentioned with liquid acid catalysts, selectivity and yield remain at an almost constant high level when the olefin space velocity (OSV) is increased. However, a critical OSV can be identified above which the polymerization reactions rapidly start to increase. This is related to the available number of add sites and the rate... 

Through this systematic study, Exelus was able to identify an optimal window of design parameter values that were then used to develop the catalyst. By judicious manipulation of the active material composition, researchers at Exelus developed a unique solid-acid catalytic system that has roughly 400% more active sites than a typical solid-acid catalyst. The catalyst activity was found to be higher than a typical liquid acid catalyst, which means that smaller amounts of catalyst are required, allowing one to design alkylation reactors with significantly lower volumes. 

Catalysts in which the active component is a metal, and solid-acid catalysts, are much used in the fine-chemical industry. Metal catalysts are generally used to perform hydrogenations and oxidations. Solid-acid catalysts can replace conventional liquid-acid catalysts, which avoids the production of waste acid. Solid-acid catalysts are usually ion-exchangers, though clay minerals and, especially, zeolites are also employed. With zeolites the shape selectivity can have additional advantages. 

Some specific factors should be considered when using zeolites as catalysts in isobutane/olefin alkylation. The first is the strong hydrocarbon adsorption of zeolites, especially at low temperatures, which makes the actual concentration of the reactants in the zeolite quite high. In addition, and due to the high concentration of acid sites in the zeolite cavities, zeolite would behave as a liquid-acid catalyst but with a high solubility of reactants. Taking this into account it can be easily assumed that the Si/Al ratio can determine the nature of reaction products. In this way, it has been proposed that zeolites... 

Due to the Clean Air Act, increasing attention is paid to the production of alkylates, which is a very clean burning fuel and has a high MON (motor octane number) with a low octane sensitivity and moderate vapor pressure. Commercially operated alkylate production uses a liquid acid catalyst such as H2SO4 or HE, resulting in problems associated with cost, apparatus and the environment [47]. New synthetic methods utilizing solid acid catalysts have been developed but no commercial process has emerged due to fast catalyst deactivation [48]. 

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