Catalytic Cracking of Polyolefins in the Molten Phase——Basic Study for the Process Development of Waste Plastics Liquefaction

The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.

Recovery of rare earths from spent FCC catalysts by solvent extraction using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(EHEHPA)

A process to recover rare earth（RE） metals from spent fluid catalytic cracking（FCC） catalysts by solvent extraction was studied, using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester（EHEHPA or P507）. The recovery process involved three steps：（1） leaching REs（mainly lanthanum and cerium）;（2） solvent extraction by applying saponified P507-kerosene system;（3） stripping. Experiments to assure optimal operating conditions were conducted. Results indicated that RE metals could be recovered effectively from spent catalyst with saponified P507-kerosene-HCl system. At room temperature of 25 oC, 10 g spent catalyst with 110 m L of HCl（1 mol/L） could achieve a leaching efficiency of 85%. For extraction, initial pH value of 3.17, organic/aqueous ratio（O/A ratio） of 2：1 with an extractants＇ saponification rate of 20% could obtain 100% efficiency. In the stripping process, 1 mol/L HCl with O/A ratio of 1：1 led to a stripping efficiency of 96%. In the present study, RE metals from spent FCC catalysts were effectively recovered, which avoided wasting a large amount of RE resources. It provides a theoretical support for commercial recycling of RE resources.

CFD simulation of gas-solid flow patterns in a downscaled combustor-style FCC regenerator

To investigate the gas-solid flow pattern of a combustor-style fluid catalytic cracking regenerator, a laboratory-scale regenerator was designed. In scaling down from an actual regenerator, large-diameter hydrodynamic effects were taken into consideration. These considerations are the novelties of the present study. Applying the Eulerian-Eulerian approach, a three-dimensional computational fluid dynamics （CFD） model of the regenerator was developed. Using this model, various aspects of the hydrodynamic behavior that are potentially effective in catalyst regeneration were investigated. The CFD simulation results show that at various sections the gas-solid flow patterns exhibit different behavior because of the asymmetric location of the catalyst inlets and the lift outlets. The ratio of the recirculated catalyst to spent catalyst determines the quality of the spent and recirculated catalyst mixing and distribution because the location and quality of vortices change in the lower part of the combustor. The simulation results show that recirculated catalyst considerably reduces the air bypass that disperses the catalyst particles widely over the cross section. Decreasing the velocity of superficial air produces a complex flow pattern whereas the variation in catalyst mass flux does not alter the flow pattern significantly as the flow is dilute.