The High Temperature Chlorination of Various Mono- and Dichloropropenes

Hearne, G. W.; Evans, Theodore W.; Yale, Harry L.; Hoff, Matthias

doi:10.1021/ja01102a037

Cited by 15 publications

(8 citation statements)

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“…Furthermore, for the high‐temperature substitutive chlorination of 3‐C 3 H 5 Cl, Hearne et al 25 proposed a rearrangement mechanism to explain the possible reason that why the major product is not 3,3‐C 3 H 4 Cl 2 or 2,3‐C 3 H 4 Cl 2 , but rather 1,3‐C 3 H 4 Cl 2 . That is, Cl · first attacks allyl chloride to form CH 2 ═CH─CHCl · and HCl.…”

Section: Experimental Results and Reaction Kinetics Modelsmentioning

confidence: 99%

“… a According to the rearrangement mechanism proposed by Hearne et al, 25 it consists of two substeps: Cl · + C 3 H 5 Cl → CH 2 CHCHCl · + HCl and CH 2 CHCHCl · → · CH 2 CHCHCl. In Table 1, C 3 H 5 Cl, C 3 H 6 Cl 2 and C 3 H 4 Cl 2 refer to 3‐C 3 H 5 Cl, 1,2‐C 3 H 6 Cl 2 , and 1,3‐C 3 H 4 Cl 2 , respectively, the structure of C 3 H 6 Cl · is CH 2 ClC · (H)CH 3 .…”

Section: Experimental Results and Reaction Kinetics Modelsmentioning

confidence: 99%

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The kinetics modeling and reactor simulation of propylene chlorination reaction process

Han

Luo

et al. 2021

AIChE Journal

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The kinetics experiments of fast reaction process of propylene chlorination at low temperature (30–90°C) and high temperature (420–480°C) are respectively conducted, and the corresponding reaction mechanisms and kinetics models are proposed. The radical mechanism at high temperature and the molecular mechanism at low temperature are found to be most likely with the experimental results. Specifically, the kinetics model, firstly considering the reversible reaction step of forming C3H6Cl· and direct hydrogen abstraction of forming C3H5·, shows better agreement with the experimental data. Furthermore, the critical reaction temperature Tcritical is firstly proposed to determine the dominant reaction mechanism in different conditions, and correspondingly the combination method of the high‐temperature and low‐temperature kinetics models has been adopted for tubular reactor simulation, which can reasonably reflect the influence of wide variation range of temperature in the reactor and guide the industrial reactor design in the further work.

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Section: Experimental Results and Reaction Kinetics Modelsmentioning

confidence: 99%

Section: Experimental Results and Reaction Kinetics Modelsmentioning

confidence: 99%

The kinetics modeling and reactor simulation of propylene chlorination reaction process

Han

Luo

et al. 2021

AIChE Journal

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“…As shown, in the case of chlorination of allyl chloride, the resonance states of the chloroallyl radical intermediates are not symmetrical and their propagation reactions lead to the two different dichloropropene isomers in an approximate 10:90 ratio (26). In addition, similar reactions result in further substitution and addition with products such as trichloropropanes, trichloropropenes, tetrachloropropanes, etc in diminishing amounts.…”

Section: Reaction Mechanismmentioning

confidence: 99%

Allyl Chloride

Kneupper

Saathoff

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Efficient and economical synthesis of allyl chloride or 3-chloropropene [107-05-1] was made possible by the discovery in the late 1930s of a direct high temperature (300-500 • C) chlorination reaction by the Shell . This synthesis allows good yields and use of common inexpensive raw materials such as propylene and chlorine. Although World War II delayed commercial implementation of this chemistry, particularly in Europe, Shell Chemical Co. was able to begin commercial production of allyl chloride in 1945 at their refinery site near Houston, which is now Deer Park, Texas (5). In 1955, The Dow Chemical Company began commercial manufacture of allyl chloride in Freeport, Texas. Initially, for both companies, the allyl chloride product was largely converted to allyl alcohol (qv) and then to glycerol (qv); however, the emergence of epoxy resins (qv) in the 1950s caused a shift to production of epichlorohydrin from allyl chloride. Both epoxy resins and glycerol can be easily produced from epichlorohydrin (6).The direct high temperature chlorination of propylene continues to be the primary route for the commercial production of allyl chloride. The reaction results in allyl chloride selectivities of 75-80% from propylene and about 75% from chlorine. Additionally, a significant by-product of this reaction, 1,3-dichloropropene, finds commercial use as an effective nematocide when used in soil fumigation. Overall efficiency of propylene and chlorine use thus is significantly increased. Remaining by-products include 1,2-dichloropropane, 2-chloropropene, and 2-chloropropane.A second method for synthesis of allyl chloride is thermal dehydrochlorination, ie, cracking, of 1,2dichloropropane, but this method is generally less satisfactory because of low allyl chloride selectivity (50-60%) and operating temperatures of 500-600 • C (4, 7-10). The by-products of cracking are 1-chloropropene and 2-chloropropene, which have no significant commercial use.The oxychlorination of propylene to allyl chloride, using hydrogen chloride and oxygen, has also been demonstrated. However, with inferior yields, less than satisfactory catalyst life, and a complex processing scheme, (11)(12)(13)(14)(15)(16)(17)(18)(19)(20) this route to allyl chloride is not utilized commercially.

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“…It is incompatible with strong oxidizers and strong acids. It is dehydrochlorinated by NaOH to give mainly 1-chloro-1-propene (45 % cis and 55 % trans isomer) [19].…”

Section: 2-dichloropropanementioning

confidence: 99%