Superacids catalysts

To solve some of the environmental problems of mixed-acid nitration, we were able to replaee sulfuric acid with solid superacid catalysts. This allowed us to develop a novel, clean, azeotropic nitration of aromatics with nitric acid over solid perfluorinated sulfonic acid catalysts (Nafion-H). The water formed is continuously azeotroped off by an excess of aromatics, thus preventing dilution of acid. Because the disposal of spent acids of nitration represents a serious environmental problem, the use of solid aeid eatalysts is a significant improvement. 

Processing heavy oils and bitumens represents a challenge for the current refinery processes, because heavy oils and bitumens poison the metal catalysts used m the refineries. In our research at the Loker Institute, we found the use of superacid catalysts, which are less sensitive to heavy oils, an attractive solution to their processing, particularly hydrocracking. 

In these (and other) solid superacid catalyst systems, bi- or multi-dentate interactions are thns possible, forming highly reactive intermediates. This amounts to the solid-state equivalent of protosolvation resulting in superelectrophilic activation. 

TaF has been characterized by ir, Raman, x-ray diffraction, and mass spectrometry (3,11,12). TaF has been used as a superacid catalyst for the conversion of CH to gasoline-range hydrocarbons (qv) (12) in the manufacture of fluoride glass and fluoride glass optical fiber preforms (13), and incorporated in semiconductor devices (14). TaF is also a catalyst for the Hquid-phase addition of HF to polychlorinated ethenes (15). The chemistry of TaF has been reviewed (1,16—19). Total commercial production for TaF is thought to be no more than a few hundred kilograms aimuaHy. 

Solid superacid catalysts, proposed as replacements for catalysts such as hydrogen fluoride and aluminum chloride for processes such as alkylation and acylation (Misono and Okuhara, 1993). 

Misono, M., and T. Okuhara (1993). Solid Superacid Catalysts. Chemtech, November, 23-29. 

Out of the metal oxides, sulfated titania and tin oxide performed slightly better than the sulfated zirconia (SZ) catalyst and niobic acid (Nb205). However, SZ is cheaper and readily available on an industrial scale. Moreover, it is already applied in several industrial processes (7,8). Zirconia can be modified with sulfate ions to form a superacidic catalyst, depending on the treatment conditions (11-16). In our experiments, SZ showed high activity and selectivity for the esterification of fatty acids with a variety of alcohols, from 2-ethylhexanol to methanol. Increasing... 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

In conclusion, more efficient and clean solid (acid and superacid) catalysts will be used in the coming years to reduce not only the emission of environmentally harmful products but also the use of noxious catalysts. The optimal catalytic systems will be determined from the nature of acid strength of its active sites, the nature of the reaction, and the reaction conditions. 

It is postulated that the facile cleavage of the complex is due to the polarization of the carbon-nitrogen double bond. At pH 7, where these investigations were carried out, the spontaneous decomposition of the Schiff base is very slow, while the metal ion-catalyzed reaction has a half life of a few minutes. Since the hydrolysis of Schiff bases is catalyzed by hydrogen ion, the metal ion catalyst can be postulated to be a superacid catalyst present in neutral solution (17, 18). 

Natural gas instead of pure methane can also be used in condensation reactions.91 When natural gas is dehydrogenated, the C2-C4 alkanes it contain are converted into olefins. The resulting methane-olefin mixture can then without separation be passed through a superacid catalyst, resulting in exothermic alkylative condensation ... 

Hydrocarbon formation from methyl chloride can be catalyzed by ZSM-5482 483 or bifunctional acid-base catalysts such as W03 on alumina.420,447 The reaction on ZSM-5 gives a product distribution (43.1% aliphatics and 57.1% aromatics at 369°C) that is very similar to that in the transformation of methanol, suggesting a similar reaction pathway in both reactions.483 W03 on A1203 gives 42.8% C2-C5 hydrocarbons at 327°C at 36% conversion.447 When using methyl bromide as the feed, conversions are comparable. However, in this case, HBr can be very readily air-oxidized to Br2 allowing a catalytic cycle to be operated. Since bromine is the oxidant, the reaction is economical. The one step oxidative condensation of methane to higher hydrocarbons was also achieved in the presence of chlorine or bromine over superacidic catalysts.357... 

It is also significant that the direct oxidative condensation of methane to higher hydrocarbons takes place in the presence of S8 over superacidic catalysts, such as TaF5 and the like.357... 

Substantial progress has been made to carry out alkylation in the gas phase over solid superacid catalysts. Nafion-H, a perfluorinated resin-sulfonic acid, for example, catalyzes the methylation of benzene and methylbenzenes with methyl alcohol under relatively mild conditions. The reaction shows low substrate selectivity.203... 

D.D. Chaudhari and R.A. Rajadhyaksha, Alkylation of o-xylene by styrene using superacid catalysts, Ind.Engg.Chem.Res., 26 (1987) 1743-45. 

The acidity of these resins, however, increases significantly by treating them with Lewis acid halides. Gates and co-workers151 153 have prepared a superacid catalyst from AICI3 and beads of macroporous, sulfonated polystyrene-divinylbenzene. The... 

Subsequently, the same authors138 described the preparation of a solid superacid catalyst with acid strength of H0 = —16 with a sulfuric acid-treated zirconium oxide. They exposed Zr(OH)4 to 1A sulfuric acid and calcined it in air at approximately 600°C. The obtained catalyst was able to isomerize (and crack) butane at room temperature. The acidity was examined by the color change method using Hammett indicators added to a powdered sample placed in sulfuryl chloride. The... 

Ways have been found to immobilize and/or to bind superacidic catalysts to an otherwise inert solid support. Several types are described in this section. 

The conventional resinsulfonic acids such as sulfonated polystyrenes (Dowex-50, Amberlite IR-112, and Permutit Q) are of moderate acidity with limited thermal stability. Therefore, they can be used only to catalyze alkylation of relatively reactive aromatic compounds (like phenol) with alkenes, alcohols, and alkyl halides. Nafion-H, however, has been found to be a suitable superacid catalyst in the 110-190°C temperature range to alkylate benzene with ethylene (vide infra) 16 Furthermore, various solid acid catalysts (ZSM-5, zeolite /3, MCM-22) are applied in industrial ethylbenzene technologies in the vapor phase.177... 

Stable nitronium salts, which are readily prepared from nitric acid (or nitrates) with HF and BF3 (and other Lewis acids such as PF5, SbF5, etc.) [Eqs. (5.171) and (5.172)], will nitrate aromatics in organic solvents generally with close to quantitative yield. Because HF and PF5 (or BF3) can be easily recovered and recycled, the method can be considered as a nitric acid nitration using a superacid catalyst [Eq. (5.173)]. 

Subsequently, selective ionic chlorination of methane to methyl chloride was achieved in the gas phase over solid superacid catalysts.526 For example, chlorination of methane in excess chlorine over Nafion-H and SbF5-graphite gave methyl chloride with 88% and 98% selectivity, respectively (185°C and 180°C, 18% and 7% conversion).527 Similarly, electrophilic bromination of alkanes has also been carried out528 (Scheme 5.53). 

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