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  • 1
    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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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Reaction kinetics and catalysis letters 62 (1997), S. 47-54 
    ISSN: 1588-2837
    Keywords: chromium orthophosphate (CrPO4) ; chromium aluminium orthophosphates (CrPO4-AIPO4) ; surface acidity, phenol/methanol and phenol/dimethyl carbonate alkylation ; activity ; selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO4 (Cr/P=1) and CrPO4-AlPO4 (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol.
    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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  • 5
    ISSN: 1588-2837
    Keywords: AlPO4 ; CrPO4 ; CrPO4−AlPO4 ; surface acidity ; 3,3-dimethyl-1-butene isomerization ; poisoning by bases ; pyridine ; 2,6-dimethylpyridine ; hexamethyldisilazane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The skeletal isomerization of 3,3-dimethyl-1-butene over AlPO4 (Al/P=1), CrPO4 (Cr/P=1), and CrPO4−AlPO4 (CrAlP, 5–10 wt.% AlPO4) catalysts is a first order reaction. Catalytic performance is affected by the precipitation agent. CrPO4 catalysts obtained in propylene oxide-aqueous ammonia showed the highest activity. Moreover, the incorporation of AlPO4 to CrPO4 developed CrAlP catalysts that exhibited increased activity, irrespective of the precipitation method, as compared with both AlPO4 and CrPO4 catalysts. Besides, CrAlP catalysts prepared in propylene oxide-aqueous ammonia were the more active ones.
    Type of Medium: Electronic Resource
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