Effect of Interphase Mass Transfer on Product Selectivity in Liquid-Phase Paraffin Chlorination

Ramage, Michael P.; Eckert, Roger E.

doi:10.1021/i260047a007

Cited by 4 publications

(10 citation statements)

References 12 publications

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“…To investigate the reaction kinetics, the variations of the methylene concentration with respect to time are plotted in Figure 4. If Equation (20) holds, the kinetics reaction of chlorination will be first order with respect to the methylene concentration. Based on this hypothesis, variations of the methylene concentration vs time should have an exponential trend.…”

Section: Study Of the Photochlorination Of Polyethylene A Moradi Et Almentioning

confidence: 99%

“…[18][19][20][21][22] In the photochlorination of tetrachloroethene, the conversion of methylene units (-CH 2 -) to chloromethylene (-CHCl-) groups has been considered the main reaction. 21,22 In the radical chlorination of polyethylene, the chlorine atoms are progressively substituted on the polyethylene backbone, which makes the kinetics study of the reaction a difficult task.…”

Section: Introductionmentioning

confidence: 99%

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Characterization and kinetics study of the photochlorination of polyethylene

Abadi

Shahrokhi

2012

Polym J

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The radical chlorination of polyethylene was carried out in perchloroethylene solvent using chlorine gas and ultraviolet photoradiation to investigate a reaction kinetics model. The recurrent structure of chloromethylene (-CHCl-) and methylene (-CH 2 -) groups and the percentage of substituted chlorine were determined using hydrogen-nuclear magnetic resonance (H-NMR) (500 MHz) spectra. A kinetics model has been proposed for this reaction in which the conversion of methylene (-CH 2 -) units to chloromethylene (-CHCl-) units was considered to be the main reaction step. The simplified version of the obtained kinetics model indicates that the reaction is first order with respect to the chlorine gas concentration and zero order with respect to the methylene concentration up to 40% chlorination. At the first stage of the reaction, the concentration of c-methylene sequences is high. Once the degree of chlorination exceeds 40%, the reaction order changes and becomes zero order with respect to the chlorine gas concentration and first order with respect to the methylene group concentration. At this stage of the reaction, the concentration of c-methylene groups has decreased considerably.

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Section: Study Of the Photochlorination Of Polyethylene A Moradi Et Almentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Characterization and kinetics study of the photochlorination of polyethylene

Abadi

Shahrokhi

2012

Polym J

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“…In the proposed mechanism, the termination reactions at the reactor wall could also be considered. However, since it is a reaction in the liquid phase and given the high reactivity of the free radicals, those reactions could be neglected (Ramage and Eckert, 1973).…”

Section: Reaction Ratementioning

confidence: 99%

“…and Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). radiation source (Ramage andEckert, 1975, 1979), the photochlorination of trichloroethylene in a stirred tank reactor irradiated from the outside by eight UV sources parallel to the reactor axis and• equally spaced one from the other (Gebhard, 1978), and the chlorination of toluene in an annular reactor of the bubbling column type with the lamp located at the axis (Yokota et al, 1981b(Yokota et al, , 1983). In the present work, a semibatch stirred tank reactor irradiated from the bottom by a UV source located at the focal axis of a cylindrical reflector of parabolic cross section has been used.…”

Section: Acknowledgmentmentioning

confidence: 99%

Modeling of a gas-liquid tank photoreactor irradiated from the bottom. 1. Theory

Alfano¹,

Cassano²

1988

Ind. Eng. Chem. Res.

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“…This coupling was first reported by van de Vusse (1966) where it was shown experimentally that mass transfer limitations in the liquid phase chlorination of n-decane affect the yield of total monochlorides. Recently, Ramage and Eckert (1973) showed that in addition to its effect on the yield of total monochlorides, mass transfer limitations also affect the yield ratio of secondary to primary monochlorides in the liquid phase chlorination of n-dodecane. Ding et al (1974) have also reported that multiple steady states can exist in liquid phase chlorination due to the high activation energy and heat of reaction.…”

mentioning

confidence: 99%