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  • 1
    ISSN: 1572-879X
    Keywords: AlPO4 ; AlPO4-Al2O3 ; surface basicity ; Langmuir adsorption ; Knoevenagel condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The amount of basic sites of A1PO4-Al2O3 (APA1-A, 5–15 wt% Al2O3) catalysts at two basic strengths was measured by studying the liquid-phase adsorption of two acidic molecules (benzoic acid (BA, pK = 4.2) and phenol (PH, pKa = 9.9) from cyclohexane solutions, through the application of a spectrophotometric method. The data obtained follow the Langmuir adsorption isotherm and the monolayer coverage at equilibrium (at 298 K),X m, is assumed as the amount of basic sites corresponding to the specific pK of the acid used as titrant. The amount of basic sites of any AlPO4-Al2O3 catalyst is higher than that of AlPO4, but lower than that of Al2O3. Besides, an increase in the Al2O3 content from 10 wt% gradually increases the basicity of the APA1-A catalyst. Moreover, calcination at increasing temperatures does not practically affect the surface basicity of APAl-A-5 and APAl-A-10 catalysts. However, for AlPO4 content higher than 10 wt% we observe a decrease in surface basicity, this decrease depends on alumina content, i.e. it is higher as the amount of alumina increases. The basic sites of APAl-A systems catalyze the Knoevenagel condensation ofp-methoxybenzaldehyde and malononitrile at room temperature and in the absence of solvent.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: AlPO4-Al2O3 ; fluoride ion loading ; surface acidity ; cyclohexene conversion ; cumene cracking ; poisoning by bases ; pyridine ; 2,6-dimethylpyridine ; hexamethyldisilazane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Brønsted acid sites on fluoride-modified AlPO4-Al2O3 (2.5 wt% F; APAl-P-2.5F) catalyst are poisoned by the presence of 2,6-dimethylpyridine (DMPY) and hexamethyldisilazane (HMDS), thus decreasing the catalytic activity for cyclohexene and cumene reaction processes, while the effect of pyridine (PY) was scarce. Besides, the drop in activity for cyclohexene conversion was accompanied by a change in reaction selectivity so that hydrogen transfer sites are much more sensitive to base poisoning (getting greater as the poisoning effect increased) than isomerization sites. Moreover, surface trimethylsilyl (TMS) complexes (formed by covalent reaction of HMDS with surface hydroxyls) decomposed and thus, the activity progressively increased at increasing time intervals, thus reaching greater values (at ca. 4 h) than the unpoisoned APAl-P-2.5F catalyst. So, DMPY was more suitable than PY and HMDS for the poisoning of Brønsted acid sites on APAl-P-F catalyst.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-879X
    Keywords: aluminum orthophosphate (AlPO4) ; AlPO4-Al2O3 ; toluene methylation ; methanol ; activity ; selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Toluene methylation with methanol over AlPO4 (AP) and AlPO4-Al2O3 (APAl) catalysts, obtained through different methods, was carried out in a continuous down-flow fixed bed reactor. The main products were xylenes (XYL), although trimethylbenzenes (TMB) were also found over APAl catalysts. The benzene and ethylbenzene selectivities increased slightly with time on stream at the expense of XYL and TMB selectivities. Isomer distribution was approximately 50, 24 and 26 mol% foro-, m- andp-XYL, and 72, 27 and 0 mol% for 1,2,3-, 1,2,4- and 1,3,5-TMB. The initial reaction rate constants were higher on APA1 catalysts and, furthermore, APAl catalysts exhibited similar catalytic activities, although those obtained in ethylene or propylene oxide are the most active ones. The same occurs on AP catalysts. Moreover, the changes in catalytic activity are similar to the changes in the acidic characteristics measured, in gas phase, versus pyridine. Furthermore, the activity decreased with time on stream due to coke deposition according to the expressionk = k0 exp(-βt). The rate of deactivation, evaluated from the deactivation coefficients (β), was greater for APAl than for AP catalysts.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Reaction kinetics and catalysis letters 63 (1998), S. 261-269 
    ISSN: 1588-2837
    Keywords: Aluminium orthophosphate (AlPO4) ; AlPO4-Al2O3 ; phenol/dimethyl carbonate alkylation ; activity ; anisole-cresol formation ; selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The vapor-phase catalytic alkylation of phenol with dimethyl carbonate over different AlPO4 (Al/P=1), Al2O3 and AlPO4-Al2O3 (5–25 wt.% Al2O3) catalysts produces anisole (O-alkylation) as the major reaction product althougho-cresol (C-alkylation) and methylanisoles were also found. The reaction is first order in phenol while O-and C-alkylation follow parallel processes. As compared with methanol, DMC is far more effective as a methylating agent, and the methylation proceeds at a lower temperature and with higher O-alkylation selectivity.
    Type of Medium: Electronic Resource
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