Javier Bilbao

University of the Basque Country | UPV/EHU · Chemical Engineering

Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process requires the use of an active and stable catalyst, but also special attention should be paid to its regene...

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 ste...

Ethanol steam reforming (ESR) over a Ni/Al2O3 catalyst prepared by reduction of a NiAl2O4 spinel is a promising alternative route to produce H2 from biomass. This work deepens into the effect of reaction conditions (450–650 °C, a steam/ethanol (S/E) ratio of 3–9, and a weight space time up to 1.3 h) and evaluates the time on stream evolution of the...

The effects that the catalyst-to-feed ratio have on the yields of products and composition of the naphtha and light cycle oil (LCO) fractions in the hydrocracking of a blend composed of high-density polyethylene (HDPE) and vacuum gasoil (VGO) using a PtPd/HY catalyst were assessed. The hydrocracking runs were carried out in a batch reactor fixing t...

An original kinetic model is proposed for the direct production of light olefins by hydrogenation of CO2/CO (COx) mixtures over an In2O3–ZrO2/SAPO-34 tandem catalyst, quantifying deactivation by coke. The reaction network comprises 12 individual reactions, and deactivation is quantified with expressions dependent on the concentration of methanol (a...

This work analyzes the effect of sorbent type (dolomite or CaO/mayenite), catalyst type (Ni/Al2O3 obtained upon reduction of a NiAl2O4 spinel or Ni/CeO2 prepared by wet-impregnation) and sorbent/catalyst ratio (4, 10 and 20) in the sorption enhanced steam reforming (SESR) of a real raw bio-oil. The experiments were performed in a continuous reactio...

The adequate configuration and the effect of the reduction was studied for the In2O3-ZrO2/SAPO-34 catalyst with the aim of improving its performance (activity and selectivity in the pseudo-steady state) for the hydrogenation of CO, CO2 and CO2/CO (COx) mixtures into olefins. The experiments were carried out in a packed bed reactor at 400 °C; 30 bar...

The use of a membrane reactor (MR) for the reforming of biomass derived oxygenates is a promising approach to produce pure hydrogen from renewable sources. In this study, a Pd membrane supported on a porous stainless-steel (PSS) tube was fabricated by Electroless Pore Plating (ELP-PP) and tested in the steam reforming (SR) of bio-oil stabilized wit...

As a consequence of the increasing greenhouse gas emissions, CO2 valorization processes are gaining importance in the last decades. Amongst the most attractive processes for CO2 utilization, its conversion into hydrocarbons stands out, in particular by means of catalytic processes with syngas co-feeding. With this purpose, an In2O3-ZrO2 (InZr) cata...

On account of the superior performance of In2O3-ZrO2/SAPO-34 tandem catalyst in the direct synthesis of olefins from CO, CO2 and CO/CO2 mixture by hydrogenation, it is interesting to establish the conditions to avoid its deactivation due to the rapid coke deposition on SAPO-34. The co-feeding of H2O and/or methanol together with H2 + CO2/CO was stu...

The direct production of C5+ hydrocarbons from CO2/CO mixtures with methanol as intermediate is an attractive alternative for the production of gasoline from CO2 and syngas derived from biomass. With this purpose, the performance of CuO-ZnO-ZrO2 (CZZ), In2O3-ZrO2 (IZ) and ZnO-ZrO2 (ZZ) metallic oxides was compared by using them in tandem with a HZS...

A six lump-based kinetic model has been developed for the hydrocracking of high-density polyethylene (HDPE) blended with vacuum gas oil (VGO) over a PtPd/HY zeolite catalyst. The blend (20 wt% HDPE and 80 wt% VGO) has been hydrocracked in a semi-continuous stirred tank reactor under the following conditions: 400–440 °C; 80 H2 bar; catalyst to feed...

Motivated by the necessity of intensifying the valorization of secondary refinery streams and of extending the life cycle of the catalysts, this study aims to obtain high quality gasoline in the hydrocracking of a pre-hydrotreated light cycle oil (HT-LCO) using noble metals catalysts supported on a spent fluid catalytic cracking (FCC) catalyst. Hyd...

The choice of appropriate reactors and reforming strategies is key to make progresses on scaling up H2 production processes from raw bio-oil. This work compares the performance (conversion, product yields and deactivation) of packed-bed and fluidized-bed reactors (PBR and FBR, respectively) using a NiAl2O4 spinel derived catalyst for the H2 product...

The valorization of post-consumer waste plastic in a refinery is an attractive initiative to avoid environmental problems caused by the poor plastic waste management. The modification of a bifunctional PtPd/HY catalyst through desilication (using NaOH) of the ultrastable HY zeolite has been carried out to upgrade waste plastic (high-density polyeth...

Different acid catalysts (silicoaluminophosphates (SAPOs) -34, −18, and − 11, and HZSM-5 zeolite) were tested as components of In2O3-ZrO2/acid tandem catalysts in the direct synthesis of light olefins by hydrogenation of CO2, CO and their mixture. The conversion and olefins yield and selectivity evidence that the presence of the large amount of str...

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 requ...

The direct synthesis of dimethyl ether (DME) is considered one of the most attractive routes for valorizing CO2 and syngas on a large scale. DME has a high cetane number and its properties are similar to those of liquefied petroleum gases (LPG). It can be used directly as fuel, selectively converted into hydrocarbons (olefins, aromatics) or used as...

A challenge for scaling up hydrogen production by raw bio-oil steam reforming (SR) is the rapid catalyst deactivation that is strongly sensitive to the temperature and bio-oil composition. This work studies the combined effect of both variables on the stability of a Ni/Al2O3 catalyst with high Ni dispersion in the internal and external surfaces of...

The effect on the energy balance of a FCC unit after co-feeding the aqueous fraction of a bio-oil together with a vacuum gas oil (VGO) has been studied. The simulation program considers the interdependency relationship between the reaction and regeneration sections in the unit, where the heat of coke combustion has to sustain the energy requirement...

The catalyst stability, mainly affected by coke deposition, remains being a challenge for the development of a sustainable process for hydrogen production by steam reforming (SR) of bio-oil. In this work, the influence of oxygenates composition in bio-oil on the deactivation by coke of a NiAl2O4 spinel derived catalyst has been approached by studyi...

The direct synthesis of dimethyl ether (DME) on bifunctional catalysts is highly attractive for valorizing CO2 and syngas derived from biomass gasification and is a key process to reduce greenhouse gas emissions. DME economy (conventionally based on its use as fuel) arouses growing interest, in parallel with the development of different routes for...

The effect of the ZrO2 content on the performance (activity, selectivity, stability) of In2O3–ZrO2 catalyst has been studied on the hydrogenation of CO2/CO mixtures. This effect is a key feature for the viability of using In2O3–ZrO2/SAPO-34 tandem catalysts for the direct conversion of CO2 and syngas into olefins via oxygenates as intermediates. Th...

This study analyzes the two step process of biomass pyrolysis and in-line steam reforming for the production of H2. In order to evaluate the effect of the volatile composition on the commercial Ni/Al2O3 catalyst performance and stability, biomass pyrolysis step was conducted at different temperatures (500-800 ºC). The analysis of the deactivated ca...

The kinetic modeling of the hydrocracking of a mixture of polystyrene (PS) and vacuum gasoil (VGO) over a PtPd/HY catalyst has been carried out. The reactions have been performed in a batch reactor under the following conditions: 380-420 °C; 80 bar; content of PS in the feed, 10 wt%; catalyst/feed ratio, 0.1 in mass; and time, 30-300 min. Different...

The upscaling of zeolitic materials to technical catalysts implies the formulation of the active phase with additives that can affect catalytic performance. As an alternative, we herein present fibrillar ZrO2/HZSM-5 composites prepared by electrospinning where HZSM-5 zeolite aggregates are joint through inert ZrO2 fibers. For zeolite loadings of 5,...

Biomass is an alternative and promising source for the sustainable production of energy and commodities such as hydrogen. For this, biomass can be converted into bioethanol through fermentation/hydrolysis that is reliably converted into hydrogen through steam reforming (SRE), and the performance of the most used catalysts for this process (Ni-based...

The catalyst regeneration is still a challenge to make the ethanol steam reforming (ESR) process feasible for sustainable H2 production. NiAl2O4 spinel derived catalysts are highly active and selective for ESR, but they require avoiding irreversible deactivation to ensure their regeneration. Their stability depends on the catalyst structure, and he...

The hydrocracking of high-density polyethylene (HDPE) blended with vacuum gas oil (VGO) has been studied to assess the effect of H2 pressure on the yield and composition of the products and with the aim of obtaining commercial fuels, mainly naphtha. The experiments have been performed using a PtPd/HY catalyst in a semibatch reactor under the follow...

The kinetics of the catalytic cracking of plastic pyrolysis oil (PPO) over three FCC (fluid catalytic cracking) equilibrium commercial catalysts has been modeled. The PPO comes from the fast pyrolysis of high-density polyethylene (HDPE). The cracking runs have been carried out in a laboratory-scale reactor under FCC conditions: 500–560 °C; catalyst...

A comparison between the behavior of Y and ZSM-5 zeolites having the same Si/Al ratio was established in the catalytic cracking of bio-oil for producing fuels and platform chemicals. The catalysts were prepared by agglomerating each zeolite with a mesoporous γ-Al2O3 matrix. Properties of the zeolites and the catalysts were characterized by N2 ads/d...

The fast deactivation of the reforming catalyst greatly conditions H2 production from biomass. In order to alleviate this problem, use of conditioning catalysts in a previous conditioning step has been proposed to modify the pyrolysis volatile stream reaching the reforming catalyst. The experimental runs have been conducted in a two-step reactor sy...

The parameters of a 6-lump kinetic model for the catalytic cracking of tire pyrolysis oil (TPO) in conditions of the industrial fluid catalytic cracking (FCC) unit have been computed. The experiments have been carried out in a riser simulator reactor, on a commercial equilibrium catalyst at the following conditions: 500–560 °C; catalyst/oil ratio (...

The upgrading of polystyrene (PS) together with vacuum gasoil (VGO) by means of hydrocracking has been investigated. The aim of the work has consisted on explaining, based on the hydrocracking mechanism, the effects of the co-feeding and of the operating conditions on products distribution and catalyst deactivation. For this purpose hydrocracking t...

The conditions for promoting the joint conversion of CO2 and syngas in the direct synthesis of light olefins have been studied. In addition, given the relevance for the viability of the process, the stability of the In2O3–ZrO2/SAPO-34 (InZr/S34) catalyst has also been pursued. The CO+CO2 (COx) hydrogenation experimental runs were conducted in a pac...

This work describes the satisfactory performance of a Ni/Al2O3 catalyst derived from NiAl2O4 spinel in ethanol steam reforming and focuses on studying the prevailing reaction routes for H2 formation in this system. NiAl2O4 spinel was synthesized using a coprecipitation method and reduced at 850 °C to obtain a Ni/Al2O3 catalyst. The spinel structure...

Bed symmetry has been analysed in fountain confined conical spouted beds operating with fine particles. Thus, vertical particle velocities and the spout shape have been determined in a wide range of spouting air velocities and bed configurations. Bed symmetry is widely accepted in the spouted beds without draft tubes or with nonporous ones, but thi...

The conversion of bioethanol into hydrocarbons, BTH process, has been simulated in reactors with different catalyst regimes (packed bed, non-circulating fluidized bed and circulating fluidized bed). The production of value-added products, as light olefins (ethylene, propylene and butenes) and gasoline (C4+ hydrocarbons), has been targeted. Differen...

Different approaches to upgrade waste plastic and vacuum gasoil (VGO) blends via hydrocracking have been investigated. The approaches have consisted on using different charges: (i) neat VGO; (ii) neat plastic pyrolysis oil (PPO); (iii) a PPO/VGO blend; (iv) a high-density polyethylene (HDPE)/VGO blend; and (v) a ternary PPO/HDPE/VGO blend. The runs...

The steam pyrolysis of pinewood sawdust has been conducted in a bench scale plant provided with a conical spouted bed reactor (CSBR). This process is of uttermost relevance for the in-line valorisation of pyrolysis volatiles, specifically for their catalytic steam reforming for hydrogen production. The influence of temperature on he product yields...

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 cat...

Biomass pyrolysis and the in-line catalytic cracking of the pyrolysis volatile stream has been approached in this study. The pyrolysis step was carried out in a conical spouted bed reactor at 500 °C, whereas the inert sand or the cracking catalysts (γ-Al2O3, spent FCC and olivine) were placed in a fixed bed reactor at 600 °C. Product analysis was c...

The yield of H2 and by-products and the heat duties in the reforming of different oxygenates in bio-oil (acids, ketones, aldehydes, phenols and saccharides) have been compared by means of thermodynamic analysis, focusing on steam reforming (SR), oxidative steam reforming (OSR) and autothermal reforming (ATR) as alternatives. The study is performed...

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 pl...

The steam reforming of bio-oil is a promising and economically feasible technology for the sustainable H2 production, yet with the main challenge of designing highly active and stable catalysts. This work aimed to study the deactivation mechanism of a NiAl2O4 spinel derived catalyst, the role of Ni and alumina sites in this mechanism and the approp...

This work studies the effect that a pre-reforming step (PSR) with low-cost catalyst (dolomite) has on the stability of a Ni-spinel catalyst in the steam reforming (SR) of raw bio-oil. PSR temperature varied in the 400–700 °C range, while SR conditions were kept at 700 °C, space-time = 0.14 gcatalysth/goxygenates, and Steam/Carbon = 3. Deactivated c...

Erregai fosilen errekuntzek eragindako klima aldaketa pairatzea da egungo gizartearen erronka nagusietariko bat. Errekuntza hauek isuritako berotegi-efektuko gasen artean ugariena karbono dioxidoa (CO2) da, hauen % 75 inguru. Beraz, honen emisioak murriztea eta dagoeneko isuritakoa bahitzea ezinbestekoa da klimaaldaketak eragindako ingurumen-kaltea...

The performance of Fe/olivine catalysts was tested in the continuous steam gasification of sawdust in a bench scale plant provided with a fountain confined conical spouted bed reactor at 850 °C. Olivine was used as catalyst support and loaded with 5 wt% Fe. The activity and stability of the catalyst was monitored by nitrogen adsorption-desorption,...

The deactivation phenomenon of HZSM-5 catalysts (SiO2/Al2O3 ratio = 30–280) in the 1-butene oligomerization has been studied. Experiments were performed in a fixed-bed reactor at 175−325 °C; 1.5−40 bar; and, 2−6 g h molC⁻¹. Used catalysts were analyzed by: temperature-programmed sweeping with N2 (TPS-N2), soluble coke analysis by gas chromatography...

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, t...

The performance of both fluidized and spouted bed reactors in the pyrolysis of waste plastics is conditioned by particle agglomeration phenomena, which worsens the quality of the gas–solid contact and eventually lead to defluidization. The objective of this work is to determine the optimum conditions for stable operation (without defluidization) in...