Heterogeneous Catalysis 2012 Heterogeneous Catalysis 2012 Solutions of Homework 4 Acid and Zeolite Catalysts

1. Using the results in these tables, explain why the three acid catalysts gave the different conversion and selectivity toward various products. Also, discuss whether or not the shape selectivity of zeolites plays role on the production of products. As shown in Table 1, HBeta showed the highest conversion among the three catalysts. As compared to HY, HBeta has lower L/B ratio, meaning that HBeta has higher Bronsted acid amount. Although HY has a higher acid density, HBeta however can generate carbenium ions more easily than HY. As a result, HBeta has higher activity in terms of conversion than HY catalyst. HZSM-5 has B/L equal to that of HBeta, which is 1, but it has lower conversion than HBeta even though it has a higher acid density. Therefore, the difference in activity of these catalysts should be ascribed to another important factor besides the acidity properties of these two catalysts. Since zeolites have stereoselectivity as a special characteristic, reactant stereoselectivity can play a role on conversion. From Table 3, among the three zeolites, HZSM-5 has the smallest pore size. Its pore size of 5.5 is not too small for phenol to get into the pore; however, the pore size of HBeta and HY is significantly bigger, so HBeta and HY allow phenol and methanol to get through more easily than HZSM-5. That explains why HZSM-5 has the lowest conversion. Note here that the size of a benzene ring is approximately 5.5 ; thus, the kinetic diameter of phenol should be in the neighborhood of 5.5 . As shown in Table 1, the selectivities of all zeolites toward cresols (especially ocresol) are comparable. Since cresols are small molecules, they can diffuse through the pores of all zeolites more easily than the other bigger products. That explains why cresols are produced in high amounts. Bulky molecules, like xylenols and methylanisoles can be produced in a much less amount. The narrower channels of HZSM-5 hinder the formation of bulky intermediates involved in both the alkylation of cresols to xylenols and the conversion of anisole by disproportionation or by alkylating phenol to cresol. However, as shown in Table 1, the ratio of o-cresol/p-cresol is considerably the same for all zeolites; thereby, indicating that the smallest pore size of HZSM-5 does not cause a significant difference on p-cresol selectivity among the formation of cresol isomers. All three zeolites have a big enough pore to allow cresols that are produced from the reactions to diffuse out of their pores but hinder the pathways of producing some bulky molecules. Thus, HZSM-5 has the smallest pore size, it hinders the pathways to produce xylenols and methylanisoles, leading to a higher selectivity of anisole (See the pathways) than those of the other two zeolites.
Sirirat Jitkarnka, Ph.D. The Petroleum and Petrochemical College Chulalongkorn University

Heterogeneous Catalysis 2012

2. Read the paper written by Jiang et al., Highly effective P-modified HZSM-5 catalyst for the cracking of C4 alkanes to produce light olefins, Appl. Catal. A: General, 340 (2008) 176182, then answer the following questions. a) How did the authors define the nature of acid sites, and using what techniques? The authors defined the nature of acid sites by two ways. The first one is based on the strength of the acid site, which is indicated by NH3-TPD (described only as strong or weak acid sites). The second one is based on the type of the acid sites, Lewis and Bronsted acid sites, which were detected by FT-IR of pyridine adsorption. Explain why NH3-TPD cannot be used to identify the type of acid sites. NH3 is a strong base that can adsorb on all types of acid sites (weak or strong). The strength of acid-base reaction is generally strong in this case. For example, it cannot be used to distinguish weak Bronsted site from strong Lewis acid site that may be simultaneously present on the surface since NH3 may desorb at the same temperature. Unless we have an evidence from another characterization to distinguish, we cannot conclude about the type of acid sites. b) What is the advantage of the introduction of P on HZSM-5 in this system? The introduction of P on HZSM-5 resulted in: The higher hydrothermal stability of framework aluminum, controlled by phosphorous-zeolite interaction in which the framework aluminum pairs are stabilized by extraframework cationic species formed by protonation of orthophosphoric acid. The lower acidity of sample. Since the strong acidity of HZSM-5 was weakened by dealumination. The formation of more surface basic site with low amount of P loaded. Higher selectivity of toward ethylene and propylene. c) What is the most important outcome from the result of CO2-TPD? The results obtained from CO2-TPD help elucidating why the lower yield of aromatics and heavier products were observed with increasing P loading. CO2 is an acidic probe that can adsorb on acid sites of catalysts. CO2-TPD therefore determines the basicity of a catalyst. When more and stronger basic sites are formed on the surface of catalysts due to P loading, the acidity and acid strength of the catalyst are suppressed; then, less carbenium ions can be generated and subsequently aromatics or heavy products cannot be easily formed from a smaller molecule of feed, like n-butane.

Sirirat Jitkarnka, Ph.D.

The Petroleum and Petrochemical College Chulalongkorn University