Search Results (22)

With the intensification of the global energy crisis, hydrogen has attracted significant attention as a high-energy-density and zero-emission clean energy source. Traditional hydrogen production methods are dependent on fossil fuels and simultaneously contribute to environmental pollution. The aqueous phase reforming (APR) of renewable biomass and its derivatives has emerged as a research hotspot in recent years due to its ability to produce green hydrogen in an environmentally friendly manner. This review provides an overview of the advancements in APR of lignocellulosic biomass as a sustainable and environmentally friendly method for hydrogen production. It focuses on the reaction pathways of various biomass feedstocks (such as glucose, cellulose, and lignin), as well as the types and performance of catalysts used in the APR process. Finally, the current challenges and future prospects in this field are briefly discussed. Full article

Cleavage of C-C bonds is crucial for hydrogen production via aqueous phase reforming of biomass-derived oxygenates. In this study, the hydrogen production performance and C-C bond cleavage capacity of Ni-W/AC catalysts with varying W/Ni ratios are evaluated using ethylene glycol as a model compound. A series of APR experiments conducted suggests that Ni-0.2W/AC catalyst exhibits the highest C₁/C₂₊ ratio of 15.87 and achieves a hydrogen yield of 47.76%. The enhanced Ni-W bimetallic interactions, which significantly improve the efficiency of C-C bond cleavage and increase catalyst activity by promoting active site dispersion, are confirmed by detailed characterization techniques. Further analysis of product distribution provides insights into the reaction pathways of ethylene glycol and the reaction mechanism for ethanol during aqueous phase reforming. All the results indicate that this catalytic reforming method effectively facilitates C-C bond cleavage and hydrogen production, contributing to a better understanding of APR mechanisms for biomass-derived oxygenates. Full article

Methanol, which can be derived from sustainable energy sources such as biomass, solar power, and wind power, is widely considered an ideal hydrogen carrier for distributed and mobile hydrogen production. In this study, a comprehensive comparison of the thermodynamic and techno-economic performance of the aqueous phase reforming (APR) and steam reforming (SR) of methanol was conducted using Aspen Plus and CAPCOST software to evaluate the commercial feasibility of the APR process. Thermodynamic analysis, based on the Gibbs free energy minimization method, reveals that while APR and SR have similar energy demands, APR achieves higher energy efficiency by avoiding losses from evaporation and compression. APR typically operates at higher pressures and lower temperatures compared to SR, suppressing CO formation and increasing hydrogen fraction but reducing methanol single-pass conversion. A techno-economic comparison of APR and SR for a distributed hydrogen production system with a 50 kg/h hydrogen output shows that although APR requires higher fixed operating costs and annual capital charges, it benefits from lower variable operating costs. The minimum hydrogen selling price for APR was calculated to be 7.07 USD/kg, compared to 7.20 USD/kg for SR. These results suggest that APR is a more economically viable alternative to SR for hydrogen production. Full article

Aqueous-phase reforming (APR) is an alternative method for treating and utilizing biogas slurry (BS) to produce renewable hydrogen from organic oxygen-containing wastewater. Considering the fluctuating characteristics of BS with changes in the degree of fermentation, developing an efficient catalyst is a major concern for the APR of BS. The novel catalyst based on molybdenum-based metal–organic-framework-derived oxides (Mo-MOF-derived α-MoO₃) was reported in this study. The results indicated that the variables (e.g., pH, organic load, and salinity) of BS corresponded to the fermentation times and exhibited decreasing trends after APR under the reaction conditions of 225 °C and 30 min. Decarboxylation was identified as the main side reaction in the APR of BS over the catalyst. An optimal yield of 2.17 mL_hydrogen/mL_BS was achieved when BS was obtained from 6 days of fermentation. Finally, the Mo-MOF-derived α-MoO₃ catalyst was obtained from the greater specific surface area of MOFs. The catalyst had a weaker acidity than the initial α-MoO₃, making it more preferred for facilitating the APR of BS. Full article

Aqueous phase reforming (APR) is a promising method for producing hydrogen from biomass-derived feedstocks. In this study, carbon-supported Pt catalysts containing particles of different sizes (below 3 nm) were deposited on different commercially available carbons (i.e., Vulcan XC72 and Ketjenblack EC-600JD) using the metal vapor synthesis approach, and their catalytic efficiency and stability were evaluated in the aqueous phase reforming of ethylene glycol, the simplest polyol containing both C–C and C–O bonds. High-surface-area carbon supports were found to stabilize Pt nanoparticles with a mean diameter of 1.5 nm, preventing metal sintering. In contrast, Pt single atoms and clusters (below 0.5 nm) were not stable under the reaction conditions, contributing minimally to catalytic activity and promoting particle growth. The most effective catalyst Pt_A/C^K, containing a mean Pt NP size of 1.5 nm and highly dispersed on Ketjenblack carbon, demonstrated high hydrogen site time yield (8.92 min⁻¹ at 220 °C) and high stability under both high-temperature treatment conditions and over several recycling runs. The catalyst was also successfully applied to the APR of polyethylene terephthalate (PET), showing potential for hydrogen production from plastic waste. Full article

Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al₂O₃ catalyst under different operating conditions. Studies were conducted at different temperatures, pressures, methanol mass fractions, and residence times. APR performance was evaluated in terms of methanol conversion, hydrogen production rate, hydrogen selectivity, and by-product formation. The results revealed that an increase in operating pressure and methanol mass fraction had an adverse effect on the APR performance. Conversely, it was found that hydrogen selectivity was unaffected by the operating pressure and residence time for the methanol feed mass fraction of 5%. For the methanol feed mass fraction of 55%, hydrogen selectivity was improved by operating pressure and residence time. The alumina support phase change to boehmite as well as sintering and leaching of the catalytic particles were observed during catalyst stability experiments. Additionally, a comparison between methanol steam reforming (MSR) and APR was also performed. Full article

Hydrogen is a clean-burning fuel with water as its only by-product, yet its widespread adoption is hampered by logistical challenges. Liquid organic hydrogen carriers, such as alcohols from sustainable sources, can be converted to hydrogen through aqueous-phase reforming (APR), a promising technology that bypasses the energy-intensive vaporization of feedstocks. However, the hydrothermal conditions of APR pose significant challenges to catalyst stability, which is crucial for its industrial deployment. This review focuses on the stability of catalysts in APR, particularly in sustaining hydrogen production over extended durations or multiple reaction cycles. Additionally, we explore the potential of ultrasound-assisted APR, where sonolysis enables hydrogen production without external heating. Although the technological readiness of ultrasound-assisted or -induced APR currently trails behind thermal APR, the development of catalysts optimized for ultrasound use may unlock new possibilities in the efficient hydrogen production from alcohols. Full article

The treatment of dairy industry effluents poses a significant challenge from the environmental point of view because of its high organic load. In this work, the aqueous phase reforming of lactose was investigated as a representative model compound for the production of renewable hydrogen. The tests were conducted using two different scenarios: the first one is referred to as direct aqueous phase reforming (APR); the second one proposed a pre-hydrogenation step, followed by APR. The implementation of this reactive pretreatment allowed for minimizing the solid by-product formation with respect to the direct APR, where most of the initial carbon ended up as solid residue. The pre-hydrogenation was investigated in the range of 180–220 °C, using Ru-based catalysts. In the best scenario (using 5% Ru/C), the carbon to solid was reduced by 95%, and up to 70% of the initial carbon was converted into gaseous compounds, hence contributing to the removal of the organic content of the wastewater while producing an energy carrier. Moreover, the hydrogen selectivity increased up to 70% (with respect to 2.5% for direct APR), thanks to hindering homogeneous reaction pathways that do not lead to hydrogen production. Finally, an energetic analysis was conducted to assess the possibility of coupling the APR with the dairy industry and quantifying the percentage of energy which may be produced in situ to satisfy industrial duties. Full article

Hydrogen from biomass, as a promising alternative fuel, is becoming considerably attractive due to its high energy density and clean emissions. The aqueous phase reforming (APR) of biomass-derived oxygenated hydrocarbons and water is a renewable and efficient pathway for hydrogen production and shows great potential. However, the key to the application of this technique is to develop catalysts with high hydrogen productivity. In this work, we first synthesized polyaniline–platinum (PANI-Pt) organo-metallic hybrid precursors and then obtained a high-loaded (~32 wt.% Pt) and highly dispersed (~3 nm Pt particles) Pt@NC−400 catalyst after pyrolysis at 400 °C, and the nanoparticles were embedded in a nitrogen-doped carbon (NC) support. The Pt@NC−400 catalyst showed an almost three times higher hydrogen production rate (1013.4 μmol_H2/g_cat./s) than the commercial 20% Pt/C catalyst (357.3 μmol_H2/g_cat./s) for catalyzing methanol–water reforming at 210 °C. The hydrogen production rate of 1,2-propanediol APR even reached 1766.5 μmol_H2/g_cat./s over the Pt@NC−400 catalyst at 210 °C. In addition, Pt@NC−400 also exhibited better hydrothermal stability than 20% Pt/C. A series of characterizations, including ICP, XRD, TEM, SEM, XPS, N₂ physisorption, and CO chemisorption, were conducted to explore the physiochemical properties of these catalysts and found that Pt@NC−400, although with higher loading than 20% Pt/C (~23 wt.% Pt, ~4.5 nm Pt particle), possessed a smaller particle size, a more uniform particle distribution, a better pore structure, and more Pt metal active sites. This study provides a strategy for preparing high-loaded and highly dispersed nanoparticle catalysts with high hydrogen productivity and sheds light on the design of stable and efficient APR catalysts. Full article

Renewable hydrogen production by aqueous phase reforming (APR) over Ni/Al-Ca catalysts was studied using pure or refined crude glycerol as feedstock. The APR was carried out in a fixed bed reactor at 238 °C, 37 absolute bar for 3 h, using a solution of 5 wt.% of glycerol, obtaining gas and liquid products. The catalysts were prepared by the co-precipitation method, calcined at different temperatures, and characterized before and after their use by several techniques (XRD, ICP-OES, H₂-TPR, NH₃-TPD, CO₂-TPD, FESEM, and N₂-physisorption). Increasing the calcination temperature and adding Ca decreased the surface area from 256 to 188 m²/g, and its value after the APR changed depending on the feedstock used. The properties of the acid and basic sites of the catalysts influenced the H₂ yield also depending on the feed used. The Ni crystallite was between 6 and 20 nm. In general, the incorporation of Ca into Ni-based catalysts and the increase of the calcination temperature improved H₂ production, obtaining 188 mg H₂/mol C fed during the APR of refined crude glycerol over Ni/AlCa-675 catalyst, which was calcined at 675 °C. This is a promising result from the point of view of enhancing the economic viability of biodiesel. Full article

Production of 1,2-propanediol and 1,3-propanediol are identified as methods to reduce glycerol oversupply. Hence, glycerol hydrogenolysis is identified as a thermochemical conversion substitute; however, it requires an expensive, high-pressure pure hydrogen supply. Studies have been performed on other potential thermochemical conversion processes whereby aqueous phase reforming has been identified as an excellent substitute for the conversion process due to its low temperature requirement and high H₂ yields, factors which permit the process of in-situ glycerol hydrogenolysis which requires no external H₂ supply. Hence, this manuscript emphasizes delving into the possibilities of this concept to produce 1,2-propanediol and 1,3-propanediol without “breaking the bank” with expenses. Various heterogenous catalysts of aqueous phase reforming (APR) and glycerol hydrogenolysis were identified, whereby the combination of a noble metal, support, and dopant with a good amount of Brønsted acid sites are identified as the key factors to ensure a high yield of 1,3-propanediol. However, for 1,2-propanediol, a Cu-based catalyst with decent basic support is observed to be the key for good yield and selectivity of product. The findings have shown that it is possible to produce high yields of both 1,2-propanediol and 1,3-propanediol via aqueous phase reforming, specifically 1,2-propanediol, for which some of the findings achieve better selectivity compared to direct glycerol hydrogenolysis to 1,2-propanediol. This is not the case for 1,3-propanediol, for which further studies need to be conducted to evaluate its feasibility. Full article

The aqueous phase reforming (APR) of glycerol was studied using sonochemically synthesized 10%Ni-x%Ca/ZrO₂ catalysts (where x = 0, 0.5, 3, and 5) for the production of value-added liquid products. The APR reaction was performed in a batch reactor under the following conditions: 20 bar, 230 °C 450 rpm, and 1 h of reaction time. The synthesized catalysts were characterized using XRD, FESEM, BET, and H₂-TPR to observe the effect of Ca doping on the physio-chemical properties of the catalysts. The results revealed that, at higher Ca loading, the catalysts experienced serious particles’ agglomeration, which resulted in a larger particles’ size, smaller surface area, and smaller pore volume owing to uneven distribution of the particles. The characterization results of the catalysts confirmed that the Us catalysts have a slightly higher surface area, pore volume, and pore size, as well as highly reducible and fine crystalline structure, compared with WI catalysts. The catalytic performance of the catalysts shows that 1,3-propanediol (1,3-PDO) and 1,2-propanediol (1,2-PDO) were the two main liquid products produced from this reaction. The highest selectivity of 1,3-PDO (23.84%) was obtained over the 10%Ni/ZrO₂ catalyst, while the highest selectivity of 1,2-PDO (25.87%) was obtained over the 10%Ni-5%Ca/ZrO₂ catalyst. Full article

Glycerol aqueous phase reforming (APR) produces hydrogen and interesting compounds at relatively mild temperatures. Among APR catalysts investigated in literature, little attention has been given to Pt supported on TiO₂. Therefore, herein we propose an innovative titania support which can be obtained through an optimized microemulsion technique. This procedure provided high surface area titania nanospheres, with a peculiar high density of weak acidic sites. The material was tested in the catalytic glycerol APR after Pt deposition. A mechanism hypothesis was drawn, which evidenced the pathways giving the main products. When compared with a commercial TiO₂ support, the synthetized titania provided higher hydrogen selectivity and glycerol conversion thanks to improved catalytic activity and ability to prompt consecutive dehydrogenation reactions. This was correlated to an enhanced cooperation between Pt nanoparticles and the acid sites of the support. Full article

The effect of catalyst loading in the Aqueous Phase Reforming (APR) of bio-oil aqueous fraction has been studied with a Ni-Co/Al-Mg coprecipitated catalyst. Because of the high content of water in the bio-oil aqueous fraction, APR could be a useful process to convert this fraction into valuable products. Experiments of APR with continuous feeding of aqueous solution of acetol, butanol and acetic acid as the only compound, together with a simulated and a real aqueous fraction of bio-oil, were carried out. Liquid products in the liquid effluent of the APR model compounds were quantified and the reaction pathways were revised. The increase of catalyst loading produced an increase of gas production and a gas with higher alkanes content. Acetol was the compound with the highest reactivity while the conversion of acetic acid was very low. The presence of acetic acid in the feed caused catalyst deactivation. Full article

Bimetallic Pt-Co catalysts derived from cobalt aluminate spinel were investigated in the liquid-phase water–gas shift (WGS) reaction and CO hydrogenation. Liquid-phase WGS is a key reaction in the aqueous-phase reforming (APR) of polyols; thus, WGS activity is essential to formulate good APR catalysts. In this work, catalysts with different Pt/Co molar ratios were synthesized together with a reference Pt/alumina. All the synthesized catalysts were characterized by various techniques in order to gain knowledge on their structural and surface characteristics. WGS activity was tested with a feedstream of CO/H₂O = 1/15 (space-time of 76.8 kg_cat·s/mol_CO), isothermal operation at 260 °C and 50 bar, for 10 TOS. Bimetallic Pt-Co catalysts showed improved activity in liquid-phase WGS in comparison to bare Co or Pt catalysts, which was ascribed to the synergistic effect. Despite being subjected to an increased hydrogen concentration in the feedstream (H₂/CO between 0 and 12/3), these catalysts maintained a preferential selectivity towards WGS activity. In addition, the effect of temperature (220–260 °C) and pressure (25–50 bar) was investigated over a catalyst with 0.3Pt/CoAl. CO conversion and CO₂ yield were more sensitive to temperature, while a higher pressure favored methane production. The measured activation energy in the 220–260 °C temperature range was 51.5 kJ/mol. Full article