Energy Analysis and Heat Integration in the Joint Process of Biomass Fast Pyrolysis and In Line Sorption Enhanced Steam Reforming.

Biomass Fast Pyrolysis and in line Steam Reforming (PY-SR) is promising alternative for H2 production. However, there are potential strategies for intensifying the process, such as capturing the CO2 in situ in the reforming step, which is so-called Sorption Enhanced Steam Reforming (SESR). Both PY-SR and PY-SESR were simulated using a thermodynamic approach and empirical correlations, and they were compared based on the energy requirements, H2 production, and H2 purity at different temperatures (500-800 °C) and steam to biomass (S/B) ratios (0-4). Then, the energy requirements for the PY-SESR were analyzed in detail for a reforming temperature of 600 °C and several S/B ratios, and a heat integration scheme was proposed, aiming at making the process thermally autosustained. Although the energy requirement of PY-SESR is always higher than that of PY-SR at the same reforming conditions, it allows the use of milder operating conditions, with the process performance being even better. Thus, PY-SESR outshines PY-SR, as it allows obtaining a higher H2 production (0.124 kgH2 kg-1 biomass vs 0.118 kgH2 kg-1 biomass) and H2 purity (98 mol % vs 67 mol %), with a lower energy requirement, and capturing the CO2 generated, thereby attaining negative emissions. The main energy demands of this process account for water evaporation and sorbent calcination. Nevertheless, a thermally autosustained PY-SESR process may be attained by recovering heat from the product streams, transferring heat from the reforming reactor to the pyrolysis reactor, and burning the char generated in the pyrolysis step.

Biomass Source Influence on Hydrogen Production through Pyrolysis and in Line Oxidative Steam Reforming.

This study evaluates the potential of several biomasses differing in nature and composition for their valorization by pyrolysis and in line oxidative steam reforming. The first task involved the fast pyrolysis of the biomasses in a conical spouted bed reactor (CSBR) at 500 °C, in which product yields were analyzed in detail. Then, the oxidative steam reforming (OSR) of pyrolysis volatiles (gases and bio-oil) was approached in a fluidized bed reactor (FBR). The reforming experiments were performed at 600 °C, with a steam/biomass (S/B) ratio of 3 and catalyst (Ni/Al2O3) space times of 7.5 and 20 gcat min gvol -1. Concerning equivalence ratio (ER), a value of 0.12 was selected to ensure autothermal operation. Remarkable differences were observed in H2 production depending on the type of biomass. Thus, pine wood led to a H2 production of 9.3 wt %. The lower productions obtained with rice husk (7.7 wt %) and orange peel (5.5 wt %) are associated with their higher ash and fixed carbon content, respectively, which limit the efficiency of biomass conversion to bio-oil. However, in the case of the microalgae, the poor performance observed is because of the lower conversion in the reforming step toward gases due to the composition of its pyrolysis volatile stream.

Appraisal of agroforestry biomass wastes for hydrogen production by an integrated process of fast pyrolysis and in line steam reforming.

The pyrolysis and in line steam reforming of different types of representative agroforestry biomass wastes (pine wood, citrus wastes and rice husk) was performed in a two-reactor system made up of a conical spouted bed and a fluidized bed. The pyrolysis step was carried out at 500 °C, and the steam reforming at 600 °C with a space time of 20 gcatalyst min gvolatiles-1 and a steam/biomass ratio (S/B) of 4. A study was conducted on the effect that the pyrolysis volatiles composition obtained with several biomasses has on the reforming conversion, product yields and H2 production. The different composition of the pyrolysis volatiles obtained with the three biomasses studied led to differences in the initial activity and, especially, in the catalyst deactivation rate. Initial conversions higher than 99% were obtained in all cases and the H2 production obtained varied in the 6.7-11.2 wt% range, depending on the feedstock used. The stability of the catalysts decreased depending on the feedstock as follows: pine wood â‰« citrus waste > rice husk. A detailed assessment of the mechanisms of catalyst deactivation revealed that coke deposition is the main cause of catalyst decay in all the runs. However, the volatile composition derived from the pyrolysis of citrus waste and rice husk involved the formation of an encapsulating coke, which severely blocked the catalyst pores, leading to catalyst deactivation during the first minutes of reaction.

On the pyrolysis of different microalgae species in a conical spouted bed reactor: Bio-fuel yields and characterization.

The aim of this work was to study fast pyrolysis of three microalgae species in a continuous bench-scale conical spouted bed reactor at 500 °C. Bio-gas, bio-oil and bio-char yields have been determined and characterized by using GC, GC/MS, elemental analyzer and SEM. Bio-oil was the main product obtained through pyrolysis of microalgae. The non-condensable gaseous stream is made up of mainly hydrogen, carbon monoxide and carbon dioxide, apart from other light hydrocarbons detected in lower concentration, as are methane, ethane, ethylene, propane and propylene. The compounds identified in the bio-oil have been categorized into hydrocarbons, nitrogen containing compounds, ketones, alcohols, acids, lactones, phenols and aldehydes. The nitrogen and carbon contents of the microalgae bio-chars are higher than those for bio-chars derived from other biomasses. Pyrolysis improved the morphology and porous structure of microalgae. Finally, the mechanism involving microalgae pyrolysis has been approached and the main reaction pathways have been proposed.

Improving bio-oil properties through the fast co-pyrolysis of lignocellulosic biomass and waste tyres.

Pinewood sawdust and the waste rubber from truck tyres have been co-pyrolysed in order to improve the properties of bio-oil for its integration in oil refineries. In addition, an analysis has been conducted of the effect the interactions between these two materials' pyrolysis reactions have on product yields and properties. Biomass/tyre mixing ratios of 100/0, 75/25, 50/50, 25/75 and 0/100 by weight percentage have been pyrolysed in continuous mode at 500 °C in a conical spouted bed reactor, obtaining oil yields in the 55.2-71.6 wt% range. Gaseous, oil and solid fractions have been characterised for the 50/50 biomass/tyre mixture, paying special attention to the oil fraction by determining its detailed composition, elemental analysis and calorific value. Co-processing enables the stabilization of the liquid, as the co-pyrolysis oil has a stable single phase, being composed mainly of water, aromatic hydrocarbons and phenols in concentrations of 14.5, 11.1 and 9.7 wt%, respectively. Adding tyre rubber to the biomass in the pyrolysis feed improves the oil's properties, as a liquid with higher carbon content and lower oxygen and water is obtained, even if sulphur content is also increased.

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 waste's 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.

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.

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.