Kinetic model of glycerol chlorination with hydrochloric acid

Lim, Jong Hun; Song, Won Seob; Woo, Sung Yul; Lee, Dong Hoon

doi:10.1007/s11814-010-0121-y

Cited by 5 publications

(8 citation statements)

References 8 publications

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“…On the basis of this mechanism, all the reactions are considered to be pseudo-second-order. The kinetic parameters determined by Luo et al 59 are summarized in Table 10. Clearly, the kinetic behavior in the presence of aqueous HCl cannot be directly compared with that in the presence of pure gaseous HCl; however, it is possible to conclude qualitatively that the presence of water decreases the hydrochlorination reaction rate.…”

Section: Reaction Scheme Reaction Mechanism and Kineticsmentioning

confidence: 99%

“…Other two different alternative mechanisms have been proposed in the literature. ,,− Bell et al suggested a mechanism, derived from an old paper, in which esterification is again the first step but, after the ester formation, they suggest the formation of a tautomeric cyclic molecule that, in the acidic environment, is converted to an acetoxonium cationic ring, which is destabilized by a chloride ion and gives monochlorohydrins after the hydrolysis of the corresponding ester, as it can be seen in the scheme depicted in Figure .…”

Section: Reaction Scheme Reaction Mechanism and Kineticsmentioning

confidence: 99%

“…Kinetic Constants Obtained by Luo et al59 for the Reactions Occurring in Glycerol Hydrochlorination Performed with HCl in Aqueous Phase, Using Acetic Acid as a Catalyst…”

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confidence: 99%

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Chemical and Technical Aspects of the Synthesis of Chlorohydrins from Glycerol

Santacesaria

Vitiello

Tesser

et al. 2013

Ind. Eng. Chem. Res.

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In the synthesis of biodiesel via the transesterification of vegetable oils, 10 wt % of glycerol is obtained as byproduct. This means that, by increasing the biodiesel production, the glycerol availability also increases and its cost goes down more and more. In order to consume the large amount of glycerol derived from biodiesel production in a profitable way, only two strategies are possible: (i) use glycerol as raw material to produce fuel additives and (ii) use glycerol as raw material to produce commodities. In the present work, we have briefly considered the first aspect while focusing, in particular, on the second opportunity by reviewing the production of chlorohydrins by glycerol hydrochlorination with HCl. Chlorohydrins are important intermediates in the production of epichlorohydrin used to produce epoxy–resins. The advantages of producing chlorohydrins by starting from glycerol instead of propene—that is, the classical route—will be discussed. The glycerol hydrochlorination reaction is catalyzed by carboxylic acids, and in this work, we describe (i) the reaction conditions normally adopted; (ii) the behavior of different catalysts proposed in the literature (concerning activity and selectivity); (iii) the reaction mechanism; (iv) the kinetic laws, reported by different authors, along with the related parameters; and (v) the role of mass transfer. A brief discussion on the best reactors for performing the reaction and some information about the different processes used to produce epichlorohydrin starting from glycerol will also be reported. Some catalysts, other than carboxylic acids, have also been briefly reviewed, although they have not been used in industrial plants until recently

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Section: Reaction Scheme Reaction Mechanism and Kineticsmentioning

confidence: 99%

Section: Reaction Scheme Reaction Mechanism and Kineticsmentioning

confidence: 99%

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Chemical and Technical Aspects of the Synthesis of Chlorohydrins from Glycerol

Santacesaria

Vitiello

Tesser

et al. 2013

Ind. Eng. Chem. Res.

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“…The chlorination of glycerol has been investigated to produce dichloropropanol [123][124][125][126] which can be used as an intermediate for epichlorohydrin. In addition, the etherification of glycerol with isobutylene has been investigated to produce an oxygenate additive which can be used as an ignition accelerator and octane booster [127].…”

Section: Reforming Of Glycerol To Valuable Chemicals By Catalysismentioning

confidence: 99%

Catalytic Technologies for Biodiesel Fuel Production and Utilization of Glycerol: A Review

et al. 2012

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More than 10 million tons of biodiesel fuel (BDF) have been produced in the world from the transesterification of vegetable oil with methanol by using acid catalysts (sulfuric acid, H 2 SO 4 ), alkaline catalysts (sodium hydroxide, NaOH or potassium hydroxide, KOH), solid catalysts and enzymes. Unfortunately, the price of BDF is still more expensive than that of petro diesel fuel due to the lack of a suitable raw material oil. Here, we review the best selection of BDF production systems including raw materials, catalysts and production technologies. In addition, glycerol formed as a by-product needs to be converted to useful chemicals to reduce the amount of glycerol waste. With this in mind, we have also reviewed some recent studies on the utilization of glycerol.

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“…Santacesaria et al [11,12,15] performed a comparison of the kinetic behavior of different catalysts (mainly carboxylic acids) and proposed a correlation between the pKa of the different acids and the activity and selectivity. Luo et al [16] and Lim et al [17] have developed a kinetic model for glycerol chlorination in the presence of acetic acid as catalyst that can be considered the reference catalyst for this reaction [12,[18][19][20][21]. The proposed kinetic model is based on a simplifying monophasic approximation that does not consider the formation of the intermediates in the chlorination reaction, such as esters formed from glycerol and the catalytic species.…”

Section: Introductionmentioning

confidence: 99%