Undoubtedly, hydrogen (H2) is a clean feedstock and energy carrier whose sustainable production should be anticipated. The pyrolysis of biomass or waste plastics and the subsequent reforming over base (transition) or noble metals supported catalysts allows reaching elevated H2 yields. However, the catalyst used in the reforming step undergoes a rapid and severe deactivation by means of a series of physicochemical phenomena, including metal sintering, metallic phase oxidation, thermal degradation of the support and, more notoriously, coke deposition. This review deals with the currently existing alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase process stability, and then delves with the fundamental phenomena occurring during this catalyst deactivation. An emphasis is placed on coke deposition and its influence on deactivation, which depends on its location, chemical nature, morphology, precursors or formation mechanism, among others. We also discuss the challenges for increasing the value of the carbon materials formed and therefore, enhance process viability.

Coke formation and deactivation during catalytic reforming of biomass and waste pyrolysis products: A review

The gasification of biomass produces a syngas that can be used for electricity generation and fuels/chemicals production. However, tar is generated along with the syngas as a by-product which causes problematic issues in the end-use of the syngas, such as blockages, plugging and corrosion. Catalytic steam reforming is a suitable option to convert tar into more syngas in the presence of nickel-based catalysts, as the preferred catalyst, mainly due to their activity and low cost. There has been considerable research reported in the literature on modified nickel-based catalysts for steam tar reforming. These modifications have been carried out in order to improve the performance of the Ni-based catalysts for tar reforming, mainly in terms of catalyst stability and activity. Such improvements are achieved by manipulating the properties of the catalyst. This paper therefore presents a critical assessment of these modifications on Ni-based catalysts available in the literature for improved tar reforming. The modifications considered in this review were categorised as: the addition of secondary metal (Fe, Co, Cu, Cr), the addition of noble metals (Pt, Pd, Rh, Au, Rh, Ir), addition of rare earth metals as promoters (Ce, La), alkali and alkaline earth metals (Sr, Ba, Ca, Mg,Ba) and modification of the support material. The paper aims at understanding the properties responsible for the improved performance of the modified Ni-based catalysts in comparison with unmodified Ni-based catalysts. The review paper will serve as a guide for further improvement of Ni-based catalysts for biomass tar reforming.

Modified nickel-based catalysts for improved steam reforming of biomass tar: A critical review

Bio-oil is a mixture of organics produced from pyrolysis of biomass. The organics in bio-oil serve as the feedstock for the production of hydrogen, chemicals, biofuels and carbon materials. In many...

Coke Formation during Thermal Treatment of Bio-oil

Hydrogen Production Technologies: From Fossil Fuels toward Renewable Sources. A Mini Review

Hydrogen production from catalytic steam reforming of biomass pyrolysis oil or bio-oil derivatives: A review

Hydrogen obtained from biomass derivatives is considered a promising alternative to fossil fuels. The aim of this work is to test the viability of Ni-M/SBA-15 (M: Co, Cu, Cr) catalysts for the hydrogen production from bio-oil aqueous fraction reforming. Tests were performed in a fixed-bed reactor at 600 °C and atmospheric pressure. Firstly, the steam reforming (SR) of acetic acid, hydroxyacetone, furfural and phenol, as representative constituents of the bio-oil aqueous fraction, was carried out. Lower reactivity with increasing carbon number and decreasing steam-to-carbon ratio was observed. Coking rate during SR is a consequence of carbon number and aromaticity of the reactant, as well as the steam-to-carbon ratio. However, deactivation also depends on the graphitization degree of carbon filaments, higher in the case of coke formed from phenol. Then, the performance of the Ni-M/SBA-15 catalysts was studied in the reforming of a bio-oil aqueous fraction surrogate containing the four model compounds. Ni-Co/SBA-15 and Ni-Cr/SBA-15 samples were the most active because Co also catalyze the steam reforming reactions and Cr promotes the formation of very small Ni crystallites accounting for high conversion and the low coke deposition (~8 times lower than Ni/SBA-15) in the form of poorly condensed carbon filaments.

https://www.mdpi.com/1422-0067/20/3/512/pdf

Steam Reforming of Model Bio-Oil Aqueous Fraction Using Ni-(Cu, Co, Cr)/SBA-15 Catalysts

Coke evolution in simulated bio-oil aqueous fraction steam reforming using Co/SBA-15

Hydrogen production derived from thermochemical processing of biomass is becoming an interesting alternative to conventional routes using fossil fuels. In this sense, steam reforming of the aqueous fraction of microalgae hydrothermal liquefaction (HTL) is a promising option for renewable hydrogen production. Since the HTL aqueous fraction is a complex mixture, acetic acid has been chosen as model compound. This work studies the modification of Co/SBA-15 catalyst incorporating a second metal leading to Co-M/SBA-15 (M: Cu, Ag, Ce and Cr). All catalysts were characterized by N2 physisorption, ICP-AES, XRD, TEM, H2-TPR, H2-TPD and Raman spectroscopy. The characterization results evidenced that Cu and Ag incorporation decreased the cobalt oxides reduction temperatures, while Cr addition led to smaller Co0 crystallites better dispersed on the support. Catalytic tests done at 600 °C, showed that Co-Cr/SBA-15 sample gave hydrogen selectivity values above 70 mol % with a significant reduction in coke deposition.

Hydrogen Production from Steam Reforming of Acetic Acid as a Model Compound of the Aqueous Fraction of Microalgae HTL Using Co-M/SBA-15 (M: Cu, Ag, Ce, Cr) Catalysts

Pedro J. Megía

Papers

Hydrogen Production Technologies: From Fossil Fuels toward Renewable Sources. A Mini Review

Steam Reforming of Model Bio-Oil Aqueous Fraction Using Ni-(Cu, Co, Cr)/SBA-15 Catalysts

Coke evolution in simulated bio-oil aqueous fraction steam reforming using Co/SBA-15

Hydrogen Production from Steam Reforming of Acetic Acid as a Model Compound of the Aqueous Fraction of Microalgae HTL Using Co-M/SBA-15 (M: Cu, Ag, Ce, Cr) Catalysts

Agglomerated Co–Cr/SBA-15 catalysts for hydrogen production through acetic acid steam reforming