Browsing by Author "Sanchez Monsalve, D. A."
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Item Open Access Chlorine removal from the pyrolysis of urban polyolefinic waste in a semi-batch reactor(Elsevier, 2020-12-11) Torres, Daniel; Jiang, Ying; Sanchez Monsalve, D. A.; Leeke, GaryThe pyrolysis of urban chlorine-containing polyolefinic plastic waste with simultaneous retention of HCl is investigated. Different chemical removers based on sodium, calcium and zinc bases, and different adsorbents based on alumina or zeolites were used inside the reactor or in downstream hot filters, respectively, for chlorine removal and upgrading of pyrolysis oils. Initially, polyolefin waste (POW, containing a 98.5 wt% polyolefins) was thermogravimetrically pyrolyzed to determine its thermal behaviour. Subsequently, chemical removers were mixed with the POW which was pyrolyzed at 480 °C in a semi-batch reactor. The adsorbents were tested separately in hot filters (300 ± 20 °C) downstream of the pyrolysis reactor. After the pyrolysis, the resulting char containing the chemical removers and the absorbents in the hot filters were analysed by FTIR, CHN elemental analysis and ESEM-EDS to determine their respective chlorine contents. The highest chlorine retention was 23.8 wt% for chemical remover when used in direct contact with POW, while a zeolite used in the hot filter (gas streams) gave a chlorine retention of 65.6 wt%. The pyrolytic liquids consisted of mixtures of C7-C40 hydrocarbons made up of olefinic and aliphatic hydrocarbons with a very low presence of aromatics (estimated to be below 3 wt% by HPLC). In most cases, the chlorine removal processes resulted in waxier pyrolytic oils and with a higher degree of branchingItem Open Access Understanding the dechlorination of chlorinated hydrocarbons in the pyrolysis of mixed plastics(American Chemical Society, 2021-01-15) Jiang, Guozhan; Sanchez Monsalve, D. A.; Clough, Peter T.; Jiang, Ying; Leeke, Gary A.The dechlorination of chlorine containing hydrocarbons in pyrolysis vapor is poorly understood. In order to shed new light on the dechlorination mechanism, a model mixture composed of iso-octane doped with 2-chlorobutane, 2-chloroethylbenzene, and chlorobenzene was used to study the dechlorination of chlorinated hydrocarbons by alkali adsorption. These three chlorinated hydrocarbons were selected as they can be typically produced from the pyrolysis of mixed plastic waste containing polyvinyl chloride (PVC). The mixture is pumped continuously through a Na2CO3 or CaCO3/alumina bed, and GC-MS is used to identify the dechlorination products and to follow the dechlorination reactions. When chlorine is bonded to an aliphatic carbon with an adjacent aliphatic hydrogen, the chlorinated compound first undergoes a dehydrochlorination reaction to form HCl and olefins, and subsequently the HCl is reacted with the alkali in the absorbents. In our experiments, 2-chlorobutane is converted to 2-butene, and 2-chloroethylbenzene is converted to styrene. The formation of HCl and subsequent reaction with alkali components in the absorbent is verified by IR spectroscopy and XRD. In the presence of an alkali, the aliphatic chlorinated hydrocarbons underwent dechlorination at a temperature of 180 °C. The removal of chlorine from aromatic chlorinated compounds operates in a different mechanism, in which the C–Cl bond scission is promoted significantly by the presence of an alumina and hydrocarbon medium. It was found that chlorobenzene undergoes dechlorination forming phenol and benzene.