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.

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.

Application of Green Polymeric Nanocomposites for Enhanced Oil Recovery by Spontaneous Imbibition from Carbonate Reservoirs.

This study experimentally investigates the effect of green polymeric nanoparticles on the interfacial tension (IFT) and wettability of carbonate reservoirs to effectively change the enhanced oil recovery (EOR) parameters. This experimental study compares the performance of xanthan/magnetite/SiO2 nanocomposites (NC) and several green materials, i.e., eucalyptus plant nanocomposites (ENC) and walnut shell ones (WNC) on the oil recovery with performing series of spontaneous imbibition tests. Scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDAX), and BET (Brunauer, Emmett, and Teller) surface analysis tests are also applied to monitor the morphology and crystalline structure of NC, ENC, and WNC. Then, the IFT and contact angle (CA) were measured in the presence of these materials under various reservoir conditions and solvent salinities. It was found that both ENC and WNC nanocomposites decreased CA and IFT, but ENC performed better than WNC under different salinities, namely, seawater (SW), double diluted salted (2 SW), ten times diluted seawater (10 SW), formation water (FW), and distilled water (DIW), which were applied at 70 °C, 2000 psi, and 0.05 wt.% nanocomposites concentration. Based on better results, ENC nanofluid at salinity concentrations of 10 SW and 2 SW ENC were selected for the EOR of carbonate rocks under reservoir conditions. The contact angles of ENC nanocomposites at the salinities of 2 SW and 10 SW were 49 and 43.4°, respectively. Zeta potential values were -44.39 and -46.58 for 2 SW and 10 SW ENC nanofluids, which is evidence of the high stability of ENC nanocomposites. The imbibition results at 70 °C and 2000 psi with 0.05 wt.% ENC at 10 SW and 2 SW led to incremental oil recoveries of 64.13% and 60.12%, respectively, compared to NC, which was 46.16%.

Plasma-Catalytic Reforming of Naphthalene and Toluene as Biomass Tar over Honeycomb Catalysts in a Gliding Arc Reactor.

Biomass gasification is a promising and sustainable process to produce renewable and CO2-neutral syngas (H2 and CO). However, the contamination of syngas with tar is one of the major challenges to limit the deployment of biomass gasification on a commercial scale. Here, we propose a hybrid plasma-catalytic system for steam reforming of tar compounds over honeycomb-based catalysts in a gliding arc discharge (GAD) reactor. The reaction performances were evaluated using the blank substrate and coated catalytic materials (γ-Al2O3 and Ni/γ-Al2O3). Compared with the plasma alone process, introducing the honeycomb materials in GAD prolonged the residence time of reactant molecules for collision with plasma reactive species to promote their conversions. The presence of Ni/γ-Al2O3 gave the best performance with the high conversion of toluene (86.3%) and naphthalene (75.5%) and yield of H2 (35.0%) and CO (49.1%), while greatly inhibiting the formation of byproducts. The corresponding highest overall energy efficiency of 50.9 g/kWh was achieved, which was 35.4% higher than that in the plasma alone process. Characterization of the used catalyst and long-term running indicated that the honeycomb material coated with Ni/γ-Al2O3 had strong carbon resistance and excellent stability. The superior catalytic performance of Ni/γ-Al2O3 can be mainly ascribed to the large specific surface area and the in situ reduction of nickel oxide species in the reaction process, which promoted the interaction between plasma reactive species and catalysts and generated the plasma-catalysis synergy.

Oxidative Fast Pyrolysis of High-Density Polyethylene on a Spent Fluid Catalytic Cracking Catalyst in a Fountain Confined Conical Spouted Bed Reactor.

The oxidative fast pyrolysis of plastics was studied in a conical spouted bed reactor with a fountain confiner and draft tube. An inexpensive fluid catalytic cracking (FCC) spent catalyst was proposed for in situ catalytic cracking in order to narrow the product distribution obtained in thermal pyrolysis. Suitable equivalence ratio (ER) values required to attain autothermal operation were assessed in this study, i.e., 0.0, 0.1, and 0.2. The experiments were carried out in continuous regime at 550 °C and using a space-time of 15 gcatalyst min gHDPE -1. The influence of an oxygen presence in the pyrolysis reactor was analyzed in detail, with special focus on product yields and their compositions. Operation under oxidative pyrolysis conditions remarkably improved the FCC catalyst performance, as it enhanced the production of gaseous products, especially light olefins, whose yields increased from 18% under conventional pyrolysis (ER = 0) to 30% under oxidative conditions (ER = 0.1 and 0.2). Thus, conventional catalytic pyrolysis led mainly to the gasoline fraction, whereas light olefins were the prevailing products in oxidative pyrolysis. Moreover, the oxygen presence in the pyrolysis reactor contributed to reducing the heavy oil fraction yield by 46%. The proposed strategy is of great relevance for the development of this process, given that, on one hand, oxygen cofeeding allows solving the heat supply to the reactor, and on the other hand, product distribution and reactor throughput are improved.

Conversion of HDPE into Value Products by Fast Pyrolysis Using FCC Spent Catalysts in a Fountain Confined Conical Spouted Bed Reactor.

Continuous catalytic cracking of polyethylene over a spent fluid catalytic cracking (FCC) catalyst was studied in a conical spouted bed reactor (CSBR) with fountain confiner and draft tube. The effect of temperature (475-600 °C) and space-time (7-45 gcat min gHDPE -1 ) on product distribution was analyzed. The CSBR allows operating with continuous plastic feed without defluidization problems and is especially suitable for catalytic pyrolysis with high catalyst efficiency. Thus, high catalyst activity was observed, with waxes yield being negligible above 550 °C. The main product fraction obtained in the catalytic cracking was made up of C5 -C11 hydrocarbons, with olefins being the main components. However, its yield decreased as temperature and residence time were increased, which was due to reactions involving cracking, hydrogen transfer, cyclization, and aromatization, leading to light hydrocarbons, paraffins, and aromatics. The proposed strategy is of great environmental relevance, as plastics are recycled using an industrial waste (spent FCC catalyst).

Progress on Catalyst Development for the Steam Reforming of Biomass and Waste Plastics Pyrolysis Volatiles: A Review.

In recent decades, the production of H2 from biomass, waste plastics, and their mixtures has attracted increasing attention in the literature in order to overcome the environmental problems associated with global warming and CO2 emissions caused by conventional H2 production processes. In this regard, the strategy based on pyrolysis and in-line catalytic reforming allows for obtaining high H2 production from a wide variety of feedstocks. In addition, it provides several advantages compared to other thermochemical routes such as steam gasification, making it suitable for its further industrial implementation. This review analyzes the fundamental aspects involving the process of pyrolysis-reforming of biomass and waste plastics. However, the optimum design of transition metal based reforming catalysts is the bottleneck in the development of the process and final H2 production. Accordingly, this review focuses especially on the influence the catalytic materials (support, promoters, and active phase), synthesis methods, and pyrolysis-reforming conditions have on the process performance. The results reported in the literature for the steam reforming of the volatiles derived from biomass, plastic wastes, and biomass/plastics mixtures on different metal based catalysts have been compared and analyzed in terms of H2 production.

Waste Refinery: The Valorization of Waste Plastics and End-of-Life Tires in Refinery Units. A Review.

This review collects a wide range of initiatives and results that expose the potential of the refineries to be converted into waste refineries. Thus, they will use their current units for the valorization of consumer society wastes (waste plastics and end-of-life tires in particular) that are manufactured with petroleum derivatives. The capacity, technological development, and versatility of fluid catalytic cracking (FCC) and hydroprocessing units make them appropriate for achieving this goal. Polyolefinic plastics (polyethylene and polypropylene), the waxes obtained in their fast pyrolysis, and the tire pyrolysis oils can be cofed together with the current streams of the industrial units. Conventional refineries have the opportunity of operating as waste refineries cofeeding these alternative feeds and tailoring the properties of the fuels and raw materials produced to be adapted to commercial requirements within the oil economy frame. This strategy will contribute in a centralized and rational way to the recycling of the consumer society wastes on a large scale. Furthermore, the use of already existing and, especially, depreciated units for the production of fuels and raw materials (such as light olefins and aromatics) promotes the economy of the recycling process.

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.

Adsorption of Amido Black 10B from aqueous solution using polyaniline/SiO2 nanocomposite: Experimental investigation and artificial neural network modeling.

The present work focused on the performance of Polyaniline/SiO2 nanocomposite for removing Amido Black 10B dye from aqueous solution. The effect of different variables, such as adsorption time, the mass of adsorbent, solution pH and initial dye concentration was studied and also was optimized by an Artificial Neural Network (ANN) method. Lagergren, pseudo-second order, Intra-particle Diffusion, Elovich and Boyd models were tested to track the kinetics of the adsorption process. The experimental data were fitted to different two-parameter, and three-parameter isotherm models, namely, Langmuir, Freundlich, Temkin, D-R, Hill, Sips and Redlich-Peterson models, and their validity was examined. The results showed that the dye adsorption process was well described by Redlich-Peterson isotherm model. Thermodynamic studies revealed that the adsorption of Amido Black 10B onto Polyaniline/SiO2 nanocomposite was endothermic. The comparison of the adsorption efficiencies obtained by the ANN model and the experimental data evidenced that the ANN model could estimate the behavior of the Amido Black 10B dye adsorption process under various conditions.

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.

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.