Catalysts acid strength

Table II. Effect of Catalyst Acid Strength on Product Distribution Feedstock Arabian Vacuum Gas Oil ...

Catalyst Acid strength //o(p a) Acid strength " TPD(10- nNH3/g) Pd content (wt%) Pore size (A) BET area (m /g)... 

The comparison of acid strength measured by the use of indicators with values predicted on the basis of Fabre data (Table A) leads to the conclusion that test reaction measurements over-estimate the catalyst acid strength. One of the reasons may be that Fabre assumes that all reactions should proceed with 100% conversion. 

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

The most important appHcation of metal alkoxides in reactions of the Friedel-Crafts type is that of aluminum phenoxide as a catalyst in phenol alkylation (205). Phenol is sufficientiy acidic to react with aluminum with the formation of (CgH O)2Al. Aluminum phenoxide, when dissolved in phenol, greatiy increases the acidic strength. It is beheved that, similar to alkoxoacids (206) an aluminum phenoxoacid is formed, which is a strong conjugate acid of the type HAl(OCgH )4. This acid is then the catalyticaHy active species (see Alkoxides, metal). 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Chemical Properties. MSA combines high acid strength with low molecular weight. Its pK (laser Raman spectroscopy) is —1.9, about twice the acid strength of HCl and half the strength of sulfuric acid. MSA finds use as catalyst for esterification, alkylation, and in the polymerisation and curing of coatings (402,404,405). The anhydrous acid is also usefijl as a solvent. 

Equation 20 is the rate-controlling step. The reaction rate of the hydrophobes decreases in the order primary alcohols > phenols > carboxylic acids (84). With alkylphenols and carboxylates, buildup of polyadducts begins after the starting material has been completely converted to the monoadduct, reflecting the increased acid strengths of these hydrophobes over the alcohols. Polymerization continues until all ethylene oxide has reacted. Beyond formation of the monoadduct, reactivity is essentially independent of chain length. The effectiveness of ethoxylation catalysts increases with base strength. In practice, ratios of 0.005—0.05 1 mol of NaOH, KOH, or NaOCH to alcohol are frequendy used. 

As might be expected intuitively, there is a relationship between the effectiveness of general acid catalysts and the acid strength of a proton donor as measured by its acic dissociation constant K. This relationship is expressed by the following equation, which is known as the Brensted catalysis law ... 

Once formed, carbenium ions can form a number of different reactions. The nature and strength of the catalyst acid sites influence the extent to which each of these reactions occur. The three dominant reactions of carbenium ions are ... 

The introduction of zeolites into the FCC catalyst in the early 1960s drastically improved the performance of the cat cracker reaction products. The catalyst acid sites, their nature, and strength have a major influence on the reaction chemistry. 

Bifunctional catalysis in nucleophilic aromatic substitution was first observed by Bitter and Zollinger34, who studied the reaction of cyanuric chloride with aniline in benzene. This reaction was not accelerated by phenols or y-pyridone but was catalyzed by triethylamine and pyridine and by bifunctional catalysts such as a-pyridone and carboxylic acids. The carboxylic acids did not function as purely electrophilic reagents, since there was no relationship between catalytic efficiency and acid strength, acetic acid being more effective than chloracetic acid, which in turn was a more efficient catalyst than trichloroacetic acid. For catalysis by the carboxylic acids Bitter and Zollinger proposed the transition state depicted by H. 

The Brpnsted coefficient a represents the sensitivity of the rate to the acid strength of the catalyst. It is a measure of the degree of proton transfer from catalyst to substrate in the transition state. For nearly all reactions where BH+ contains acidic N-H or O-H groups, a is in the range 0-1. 

In general acid catalysis, the rate is increased not only by an increase in [SH ] but also by an increase in the concentration of other acids (e.g., in water by phenols or carboxylic acids). These other acids increase the rate even when [SH ] is held constant. In this type of catalysis the strongest acids catalyze best, so that, in the example given, an increase in the phenol concentration catalyzes the reaction much less than a similar increase in [H30 ]. This relationship between acid strength of the catalyst and its catalytic ability can be expressed by the Breasted catalysis equation ... 

The catalyst acidity is determined by the number of acid sites and their acid strength. The total concentration of acid sites, C<, can be obtained from independent TPD measurements. The average acid strength of the sites is characterized by the alkene standard protonation enthalpy,, and is typically determined by regression using reference... 

As shown in Fig. 2, the NH3 TPD technique provides information on acid sites over catalysts. While Al-MCM-41-P and Al-MCM-41-D have almost the same acid strengths due to their similar temperature peak of around 250°C, Al-MCM-41-P has more acid sites compared to Al-MCM-41-D. It can be gleaned from this result that the catalytic activity of Al-MCM-P is better than that of Al-MCM-D not because of Al-MCM-P s acid strength but because it has more acid sites. The oil products over... 

We have explored rare earth oxide-modified amorphous silica-aluminas as "permanent" intermediate strength acids used as supports for bifunctional catalysts. The addition of well dispersed weakly basic rare earth oxides "titrates" the stronger acid sites of amorphous silica-alumina and lowers the acid strength to the level shown by halided aluminas. Physical and chemical probes, as well as model olefin and paraffin isomerization reactions show that acid strength can be adjusted close to that of chlorided and fluorided aluminas. Metal activity is inhibited relative to halided alumina catalysts, which limits the direct metal-catalyzed dehydrocyclization reactions during paraffin reforming but does not interfere with hydroisomerization reactions. 

As an additional probe of metal activity, we monitored benzene hydrogenation activity. As seen in Figure 9, Pt-containing rare earth catalysts have lower hydrogenation activity than chlorided alumina catalysts this result reflects inhibition of metal activity on these supports relative to conventional transitional alumina supports. Whereas the acid strength can be adjusted close to that of chlorided and flourided aluminas, metal activity is somewhat inhibited on these catalysts relative to halided aluminas. This inhibition is not due to dispersion, and perhaps indicates a SMSI interaction between Pt and the dispersed Nd203 phase. 

Catalytic resnlts are well correlated with the acid strength of the active species irrespective of their natnre (Lewis or Bronsted). On the other hand, there is no clear correlation between the density of the active sites and the catalytic performances. While the FS03H/Si02 catalyst is very active (yields 99.5 -100%, Table 48.2), AICI3/MCM shows only moderate yields (14.3-20.1%) to N-acylsulfonamide, even if both samples exhibit a similar density (25 x lO , Table 48.1). 

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