1985
DOI: 10.1135/cccc19851168
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Perturbation of steady-state catalytic dehydration of alcohols by pulses of water and other substances

Abstract: The dynamic behaviour of systems consisting of 2-propanol or tert-butanol and of a solid dehydration catalyst has been studied by means of pulses of the alcohols, water, nitrogen or carbon dioxide, respectively, introduced onto fresh catalyst surface in a stream of nitrogen, or onto the working surface. The catalysts employed were alumina, alumina modified by fluoride, sulphate or sodium ions, respectively, thoria, silica-alumina, phosphotungstic acid and a sulphonated styrene-divinylbenzene copolymer. The pos… Show more

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Cited by 6 publications
(4 citation statements)
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“…9 In the particular case of the dehydration of alcohols on aluminic materials, a domain that has been widely investigated both experimentally 28−47 and theoretically, 48−52 the issue of the interactions between adsorbed species has been raised in a number of studies. Water formed during the reaction and readsorbed on the catalyst is postulated either as an inhibitor of the reaction 20,21,28,[41][42][43]52 or as a potential anchoring site for incoming alcohol. 31,53 Interactions between coadsorbed alcohol molecules are obviously required for the bimolecular formation of ether 29,35,47,50,51 but have sometimes been proposed to have inhibiting effects on the dehydration reaction.…”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…9 In the particular case of the dehydration of alcohols on aluminic materials, a domain that has been widely investigated both experimentally 28−47 and theoretically, 48−52 the issue of the interactions between adsorbed species has been raised in a number of studies. Water formed during the reaction and readsorbed on the catalyst is postulated either as an inhibitor of the reaction 20,21,28,[41][42][43]52 or as a potential anchoring site for incoming alcohol. 31,53 Interactions between coadsorbed alcohol molecules are obviously required for the bimolecular formation of ether 29,35,47,50,51 but have sometimes been proposed to have inhibiting effects on the dehydration reaction.…”
Section: Introductionmentioning
confidence: 99%
“…In the particular case of the dehydration of alcohols on aluminic materials, a domain that has been widely investigated both experimentally and theoretically, the issue of the interactions between adsorbed species has been raised in a number of studies. Water formed during the reaction and readsorbed on the catalyst is postulated either as an inhibitor of the reaction ,,, , or as a potential anchoring site for incoming alcohol. , Interactions between coadsorbed alcohol molecules are obviously required for the bimolecular formation of ether ,,,, but have sometimes been proposed to have inhibiting effects on the dehydration reaction. , Determining where and how these interactions establish on the surface, and to what extent they influence the catalyst activity and the alkene/ether selectivity as conversion increases (i.e., as less and less alcohol and more and more water competing for adsorption are present in the gas phase) is a challenging question that has not yet been addressed satisfactorily.…”
Section: Introductionmentioning
confidence: 99%
“…This peculiar behavior is called the ''stop effect'', and its only explanation is that the alkene precursor is stored on the catalyst surface during the previous (steady-state) period. In the pulse-flow regime, a pulse of an alcohol on alumina first yields a wave of water, followed by a wave of the alkene [62,63]. Further investigations using other transient and infra-red (IR) techniques showed [64][65][66] that the surface hydroxyl groups can be replaced by alkoxyl groups via the reactions with alcohols and ethers.…”
Section: Stop Effectmentioning
confidence: 99%
“…This failure is probably caused by the simplified assumptions adopted for the derivation of the Langmuir-Hinshelwood kinetics and the strong interactions of the reacting substances with the surface of alumina. Transient kinetic studies indicate [61][62][63][64][65][66] that the number of active sites is not constant but rather depends on the partial pressures of the alcohol, ether, and water (i.e., in a steady-state situation) on conversion.…”
Section: Kineticsmentioning
confidence: 99%