Stefano Stendardo

Comparison of global models of sub-bituminous coal devolatilization by means of thermogravimetric analysis

Coal gasification and combustion are strongly dependent on devolatilization step. Aim of this work is to obtain the parameters of global kinetics of devolatilization of a sub-bituminous coal with high sulfur content. The kinetic parameters are obtained by means of TG experimental data, and applying different approaches to extrapolate the data to industrial relevant conditions. The simpler method is a model-free one which supposes a single step process whose Arrhenius kinetic parameters (A and Ea) have to be determined. Another common approach is the distributed activation energy model (DAEM) which assumes a series of first order parallel reactions occurring and sharing the same pre-exponential factor, A, with a continuous distribution of the activation energy. For the fitting of the experimental data, a numerical solution to DAEM and two approximate methods have been evaluated. Moreover, the results of these kinetic methods based on empirical approaches were compared with simulated data obtained using a more complex model based on percolation theory with cross-linking mechanism and vapor–liquid equilibrium (chemical percolation devolatilization, CPD model), which allows to simulate the coal pyrolysis from volatile yield data.

Pyrolysis of WEEE plastics using catalysts produced from fly ash of coal gasification

Catalytic pyrolysis of thermoplastics extracted from waste electrical and electronic equipment (WEEE) was investigated using various fly ash-derived catalysts. The catalysts were prepared from fly ash by a simple method that basically includes a mechanical treatment followed by an acid or a basic activation. The synthesized catalysts were characterized using various analytical techniques. The results showed that not treated fly ash (FA) is characterized by good crystallinity, which in turn is lowered by mechanical and chemical treatment (fly ash after mechanical and acid activation, FAMA) and suppressed almost entirely down to let fly ash become completely amorphous (fly ash after mechanical and basic activation FAMB). Simultaneously, the surface area resulted increased. Subsequently, FA, FAMB and FAMA were used in the pyrolysis of a WEEE plastic sample at 400°C and their performance were compared with thermal pyrolysis at the same temperature. The catalysts principally improve the light oil yield: from 59 wt.% with thermal pyrolysis to 83 wt.% using FAMB. The formation of styrene in the oil is also increased: from 243 mg/g with thermal pyrolysis to 453 mg/g using FAMB. As a result, FAMB proved to be the best catalyst, thus producing also the lowest and the highest amount of char and gas, respectively.

Influence of temperature on oxygen permeation through ion transport membrane to feed a biomass gasifier

Oxygen-permeable perovskite membranes with mixed ionic-electronic conducting properties can play an important role in the high temperature separation of oxygen from air. A detailed design of a membrane test module is presented, useful to test mechanical resistance and structural stability of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) capillary membrane in the reactor environment. Preliminary experimental results of membrane permeation tests highlight the positive effect of temperature on perovskite materials. This behaviour is also confirmed by a computational model of char combustion with oxygen permeated through the membrane module, when it is placed inside a gasifier reactor to provide the necessary input of heat to the gasification endothermic process. The results show that the temperature affects the oxygen permeation of the BSCF membrane remarkably.

Steam-O2 coal gasification in the Italian ZECOMIX bubbling fluidized bed gasifier unit: Spent bed material characterization

Steam-O2 coal gasification in bubbling fluidized bed gasifier of the Italian ZECOMIX platform has been tested. A South American anthracite coal is gasified around 850 C using steam/carbon ratio near unity and catalytic olivine as bed material. Two experimental runs are conducted to assess the repeatability of gathered results. The gas stream from the reactor exit is sampled through a heated and filtering gas sampling probe and dried before on-line gas chromatographic measurements of H2, CO, CO2, and CH4 non-condensable gases. The product gas can be monitored stand alone during a very long-term. The mean composition of the producer syngas between two runs varies in the range 38-43 H2, 38-39 CO, 19-22 CO2, and 1-3 CH4 vol.% on dry basis, whereas repeatability is within 15 vol.%. The solid matter remaining in bed reactor is composed by bottom-ashes, spent olivine with some agglomerates and coarse residual char particles. Fine particulates (size less than 250 μm) separated from flue gas through cyclone process, is mainly composed of unreacted char.