Gartzen Lopez

Upgrading the rice husk char obtained by flash pyrolysis for the production of amorphous silica and high quality activated carbon.

The overall valorization of rice husk char obtained by flash pyrolysis in a conical spouted bed reactor (CSBR) has been studied in a two-step process. Thus, silica has been recovered in a first step and the remaining carbon material has been subjected to steam activation. The char samples used in this study have been obtained by continuous flash pyrolysis in a conical spouted bed reactor at 500°C. Extraction with Na2CO3 allows recovering 88% of the silica contained in the rice husk char. Activation of the silica-free rice husk char has been carried out in a fixed bed reactor at 800°C using steam as activating agent. The porous structure of the activated carbons produced includes a combination of micropores and mesopores, with a BET surface area of up to 1365m(2)g(-1) at the end of 15min.

Kinetics of scrap tyre pyrolysis under vacuum conditions.

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene-butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12K in the reaction starting temperature. The kinetic constant at 503K for devolatilization of volatile additives at 0.25atm is 1.7 times higher than that at 1atm, and that corresponding to styrene-butadiene rubber at 723K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability. The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.

Flash pyrolysis of forestry residues from the Portuguese Central Inland Region within the framework of the BioREFINA-Ter project.

The feasibility of the valorization by flash pyrolysis of forest shrub wastes, namely bushes (Cytisus multiflorus, Spartium junceum, Acacia dealbata and Pterospartum tridentatum) has been studied in a conical spouted bed reactor operating at 500 °C, with a continuous biomass feed and char removal. High bio-oil yields in the 75-80 wt.% range have been obtained for all of the materials, with char yields between 16 and 23 wt.% and low gas yields (4-5 wt.%). Bio-oils are composed mainly of water (accounting for a concentration in the 34-40 wt.% range in the bio-oil), phenols, ketones, acids and furans, with lower contents of saccharides, aldehydes and alcohols. Although their composition depends on the raw material, the compounds are similar to those obtained with more conventional feedstocks.

Fast pyrolysis of eucalyptus waste in a conical spouted bed reactor.

The fast pyrolysis of a forestry sector waste composed of Eucalyptus globulus wood, bark and leaves has been studied in a continuous bench-scale conical spouted bed reactor plant at 500°C. A high bio-oil yield of 75.4 wt.% has been obtained, which is explained by the suitable features of this reactor for biomass fast pyrolysis. Gas and bio-oil compositions have been determined by chromatographic techniques, and the char has also been characterized. The bio-oil has a water content of 35 wt.%, and phenols and ketones are the main organic compounds, with a concentration of 26 and 10 wt.%, respectively. In addition, a kinetic study has been carried out in thermobalance using a model of three independent and parallel reactions that allows quantifying this forestry wastes content of hemicellulose, cellulose and lignin.

Styrene recovery from polystyrene by flash pyrolysis in a conical spouted bed reactor.

Continuous pyrolysis of polystyrene has been studied in a conical spouted bed reactor with the main aim of enhancing styrene monomer recovery. Thermal degradation in a thermogravimetric analyser was conducted as a preliminary study in order to apply this information in the pyrolysis in the conical spouted bed reactor. The effects of temperature and gas flow rate in the conical spouted bed reactor on product yield and composition have been determined in the 450-600°C range by using a spouting velocity from 1.25 to 3.5 times the minimum one. Styrene yield is strongly influenced by both temperature and gas flow rate, with the maximum yield being 70.6 wt% at 500°C and a gas velocity twice the minimum one.

Characterization of the Liquid Obtained in Tyre Pyrolysis in a Conical Spouted Bed Reactor

Used tyres pose a serious environmental problem and pyrolysis is considered one of the more feasible solutions that may be economically profitable on a large scale. In this study the pyrolysis of tyres has been carried out in a conical spouted bed reactor at 500 °C and the liquid product has been characterized taking into account composition, heat value and simulated distillation. The tyre mass feed in each run was 2 g and the bed was made up of 15 g of sand. Pyrolysis of scrap tyre at the 500 °C gives way to a yield of 3.1% of gases, 37.6% of liquid fraction (C5-C10 range hydrocarbons), 25.6% of tar (C11+) and 33.7% of char. The liquid fraction is of suitable quality for its use as fuel but the char requires activation for its upgrading.

Catalytic Pyrolysis of High Density Polyethylene on a HZSM-5 Zeolite Catalyst in a Conical Spouted Bed Reactor

HDPE has been pyrolysed at 450 °C and 500 °C using HZSM-5 zeolite as a catalyst. Batch runs have been carried out at atmospheric pressure in a conical spouted bed reactor. Product analysis has been carried out by means of a GC, connected on-line with a thermostated line. The degradation rate of the plastic is slightly faster at 500 °C than at 450 °C and much faster than thermal pyrolysis in both cases. Products have been grouped into five lumps: the lump of light olefins, C2-C4; light alkanes, C1-C4; the gasoline fraction, C5-C11 compounds; C11+ hydrocarbons; and the coke deposited on the catalyst. An HZSM-5 catalyst is appropriate to obtain light olefins; about 55 wt% in both cases. The yield of gasoline fraction is also considerable and although its composition is not suitable for commercial gasoline, is interesting for its use in petrochemistry. The catalyst deactivation rate is low.

Efecto del uso de Catalizadores Ácidos Sobre la Distribución de Productos en la Pirólisis de Neumáticos

The thermal and catalytic pyrolysis of tyres in a high heating rate commercial microreactor has been studied by following two reaction strategies: in situ catalytic and thermal pyrolysis followed by on-line catalytic pyrolysis. The catalysts have been prepared based on HZSM-5, HY and HBeta zeolites and they have been used in situ in the pyrolysis reactor and on-line, in a fixed bed reactor. The use of the catalyst in situ decreases the pyrolysis temperature by 50 K (from 773K to 723 K) and significantly increases the yield of gas and C10- light aromatics. The shape selectivity of HZSM-5 zeolite and the higher micropore size and hydrogen transfer capacity of HY zeolite significantly affect product distribution. The HBeta zeolite catalyst has an intermediate behaviour. The yields of gases, C10aromatics and tar increase in the catalytic reforming of thermal pyrolysis.