Acid site concentration

The liquid-phase dehydration of 1-hexanol and 1-pentanol to di-n-hexyl ether (DNHE) and di-n-pentyl ether (DNPE), respectively, has been studied over H-ZSM-5, H-Beta, H-Y, and other zeolites at 160-200°C and 2.1 MPa. Among zeolites with a similar acid sites concentration, large pore H-Beta and H-Y show higher activity and selectivity to ethers than those with medium pores, although activity of H-ZSM-5 (particularly in 1-pentanol) is also noticeable. Increased Si/Al ratio in H-Y zeolites results in lower conversion of pentanol due to reduced acid site number and in enhanced selectivity to ether. Selectivity to DNPE is always higher than to DNHE... 

From Table 2 it can also be observed that the selectivity towards different hydrocarbon groups strongly depended on the acid properties of solids. Large amounts of C4 and C6 olefins were obtained for the mesoporous NiMCM-41 and NiMCM-48 catalysts with the lowest acid site concentration. In this case, a near Schulz-Flory-type product distribution (C4>C6>C8>Cio) was observed. The increase in acid site density (for the catalysts NiY, NiMCM-36, NiMCM-22) results in decrease of C 6/C8 ratio. These results are in agreement with the reaction network proposed in Scheme 1. 

Zeolites exhibit a considerably lower proton (acid site) concentration than liquid acids. For example, 1 g of H2SO4 contains 20 X 10-3 moles of protons, whereas 1 g of zeolite HY, with a Si/Al atomic ratio of five, contain no more than 3 X 10-3 moles of protons. (Note that this is a cmde approximation of the acidic sites available for catalysis, because it assumes that with both materials all protons are available and catalytically active.) Moreover, 1 g of H2SO4 occupies far less volume (i.e., 0.5 cm3) than the equivalent mass of zeolite (4-6 cm3). 

It has been suggested that the reason for this difference is the different site density. According to this proposal, the large concentration of acid sites in synthetic faujasite (ca. 5 meq/g) favors the bimolecular disproportionation reaction relative to the monomolecular isomerization. By contrast, ZSM-5 has a low acid site concentration, typically less than 0.5 meq/g. 

The relationship of Lewis and Brpnsted acid site concentrations on H—Y zeolite was explored further in a study by Ward (156) of the effect of added water. At low calcination temperatures (<500°C) only a small increase in the Brpnsted acid site concentration occurred upon addition of water to the sample. Rehydration of samples dehydroxylated by calcination above 600°C resulted in a threefold increase in the amount of Brpnsted-bound pyridine. However, no discreet hydroxyl bands were present in the infrared spectrum after rehydration. Thus, the hydroxyl groups reformed upon hydration must be in locations different from those present in the original H—Y zeolite, which gave rise to discreet OH bands at 3650 and 3550 cm-1. 

Further acid site strength and concentration measurements were reported by Morita et al. (164), who related the acidity measurements to various catalytic reactions. Using Y zeolite (Linde SK-40, 90% H form) activated at 450°C, they observed no acid sites stronger than an H0 of -8.2, although the total acid site concentration was almost twice that of the former investigations (Fig. 21, curve 4). They also measured acid site concentration as a function of decomposition temperature for NH4Y, and found that n-butylamine titration values paralleled results obtained from pyridine adsorption studies (41,151). The maximum total acidity occurred... 

Figure 21 illustrates some of the difficulties in comparing the results of different investigations. Although the four zeolite samples shown fall within a relatively narrow range of compositions, the measured total acid site concentrations differ by as much as 250%. In addition the acid sites of... 

Ai (140) measured the acid site concentration by the adsorption of ammonia. No correlation was found between the P/V ratio, the acidity, and the catalytic activity. This result has been attributed to the use of ammonia as a probe molecule that cannot distinguish between Lewis and Br0nsted acidity. Comaglia et al. (137) measured the acid sites using pyridine and acetonitrile as probes. However, the pyridine results showed no correlation between the Lewis to Br0nsted acid site ratio or the Lewis acid site concentration and the activity and selectivity of the catalyst for MA formation. 

Ai measured the acid site concentration by the adsorption of ammonia [85]. No correlation was found between the P/V ratio, the acidity and the catalytic activity. 

The chemical reagents used for the preparation of stock solutions were reagent grade and were used without further purifieation. The chemicals were in the form of the nitrate salts and were obtained eommercially from Aldrich or Fluka. Pure ceria samples were prepared by precipitation of ceria from aqueous solutions containing O.OIM Ce by adding 1 M NH3 solution. The precipitate was dried at 523K. The surface acid sites concentration was measured using Hammett titrations, with phenolphthalein as indicator, and a O.IM NaOH solution as base. 

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