Steam reforming of propionic acid: Thermodynamic analysis of a model compound for hydrogen production from bio-oil

The thermodynamic equilibrium of steam reforming of propionic acid (HPAc) as a bio-oil model compound was studied over a wide range of reaction conditions (T = 500–900 °C, P = 1–10 bar and H₂O/HPAc = 0–4 mol/mol) using non-stoichiometric equilibrium models. The effect of operating conditions on equilibrium conversion, product composition and coke formation was studied. The equilibrium calculations indicate nearly complete conversion of propionic acid under these conditions. Additionally, carbon and methane formation are unfavorable at high temperatures and high steam to carbon (S/C) ratios. The hydrogen yield versus S/C ratio passes a maximum, the value and position of which depends on temperature. The thermodynamic equilibrium results for HPAc fit favorably with experimental data for real bio-oil steam reforming under same reaction conditions.     

Kinetic investigation on butanol steam reforming over Ru/Al2O3 catalyst

Steam reforming of biomass-derived oxygenates is an attractive technique for the renewable production of hydrogen (H₂). In this work, steam reforming of n-butanol – a representative of bio-oxygenates – was studied over commercial 5% Ru/Al₂O₃ catalyst in a fixed-bed reactor. Kinetics of butanol reforming was investigated between temperatures 623 and 773 K at steam/carbon (S/C) ratio equal to 33.3 mol/mol. The W/F_A0 ratio (W: mass of catalyst, F_A0: molar flow rate of butanol in feed) was varied between 3.3 and 16.7 g h/mol. At T = 773 K, butanol conversion and H₂ yield were 93.4% and 0.61 mol/mol. Evaluation of the kinetic data showed that reaction order with respect to butanol was unity. The activation energy for the investigated reaction was 78 kJ/mol. Finally, a Langmuir-Hinshelwood model that assumed the surface reaction between the adsorbed reactants as rate-determining was used to describe the kinetic data.     

Nickel supported on low-rank coal for steam reforming of ethyl acetate

Ethyl acetate is a volatile organic compound (VOC) that has emerged as a major environmental pollutant and also one of representative components of bio-oil. In this study, mostly metallic Ni particles (size: <10 nm) were finely dispersed on low-rank coal (LRC) by the ion-exchange process. Catalytic steam reforming of ethyl acetate (EA) was performed over Ni supported on Eco LRC (Ni/Eco) to reduce EA emissions and simultaneously produce H₂. EA reforming over 17.7 wt% Ni/Eco at 400 °C results in H₂ yield of 70%–80%; this is comparable to that achieved with reforming over commercial Ni/Al₂O₃. Advantageously, metallic Ni particles are dominant over Ni oxides on LRC, and therefore, the pre-reduction step routinely required for an alumina-supported catalyst can be skipped. Furthermore, deactivation by coking is slower with Ni/Eco than with Ni/Al₂O₃ during long-term operation, probably because of the smaller particle size and preferential adsorption on the coal support.     

Hydrogen production by steam reforming of model bio-oil using structured Ni/Al2O3 catalysts

This study focuses on hydrogen production from the steam reforming of model bio-oil over Ni/Al₂O₃ catalysts prepared in two different geometries (monolith and pellet) using the dip-coating and wet impregnation methods and characterized using Powder X-Ray diffraction, Temperature Programmed Reduction, Scanning Electron Microscopy (SEM) and BET Surface area analysis. The effects of the catalyst geometry and reforming temperatures were studied by carrying out experiments at the optimal conditions of T = (823, 923, 1023) K and S/C ratio = 13 determined from the thermodynamic analysis of the process prior to the experiments using the process simulator PRO-II. The experimental results showed high steady state H₂ yield corresponding to 2.58 and 1.73 mol (out of 5.13 mol) using monolithic and the pelletized catalysts respectively. The product distribution achieved with the monolithic catalyst was closer to the thermodynamic results suggesting a higher selectivity to hydrogen production.     

Steam reforming of toluene as model biomass tar to H2-rich syngas in a DBD plasma-catalytic system

Biomass tar is one of the most troublesome issues limiting the further development of biomass pyrolysis and gasification. In this study, a plasma enhanced catalytic steam reforming technology was applied for biomass tar removal. Toluene was selected as biomass tar surrogate. The nano-sized alumina-supported nickel and iron catalysts with different molar ratios of M/Al (M: Ni or Fe, 0:1, 1:3, 1:1, 3:1, 1:0) were prepared for catalytic steam reforming of toluene in a non-thermal plasma reactor featuring dielectric barrier discharge (DBD). The results showed that syngas was the dominant gas product of toluene decomposition. The conversion efficiency of toluene and energy efficiency using Ni-Al and Fe-Al catalysts both followed a sequence: M1Al3 > M1Al1 > M3Al1, which is in line with the BET surface area and pore volume. However, the selectivity of H₂ and CO catalysed by Ni-Al and Fe-Al catalysts follows the order of M1Al3 < M1Al1 < M3Al1. Presumably, toluene dissociation is a process composed of adsorption-reaction-desorption. The formation of syngas is supposed to proceed as a series of ionic and free radical reactions occurring preferably in the gas phase. Ni1Al3 catalyst shows the largest potential in converting biomass tar into H₂-rich syngas, with a maximum toluene conversion of 96% and a largest H₂ yield of 2.18 mol/mol-toluene. Besides, the results showed that this hybrid plasma-catalysis system was potential in anti-carbon deposition.     

Hydrogen production from methanol steam reforming over Al2O3- and ZrO2-modified CuOZnOGa2O3 catalysts

New CuOZnOxGa₂O₃–Al₂O₃ and CuOZnOxGa₂O₃–ZrO₂ (CuZnxGaAl, CuZnxGaZr) catalysts with different Ga contents were prepared and tested in the methanol steam reforming reaction (MSR) under stoichiometric methanol/water = 1 mol ratio (S/C = 1) at 523 K and 548 K. Addition of Al₂O₃ or ZrO₂ components increases the surface area and modifies the reducibility of CuOZnOGa₂O₃ catalysts; the CuZnxGaZr systems showed the highest reducibility. The performance of CuOZnOGa₂O₃-based catalysts for MSR is improved by the presence of ZrO₂ promoter. CuZn3GaZr catalyst showed a high performance for MSR at 523 K and 548 K under stoichiometric conditions (S/C = 1). The catalyst resulted highly stable and selective for H₂ production, with formation of less than 0.3% mol of CO at 523 K. CO is produced as a secondary by-product through the reverse water gas shift reaction. The new catalysts show high resistance to carbon formation at the temperatures analyzed under stoichiometric conditions (S/C = 1).     

Enhancement of the quality of syngas from catalytic steam gasification of biomass by the addition of methane/model biogas

In this study, methane and model biogas were added during the catalytic steam gasification of pine to regulate the syngas composition and improve the quality of syngas. The effects of Ni/γ-Al₂O₃ catalyst, steam and methane/model biogas on H₂/CO ratio, syngas yield, carbon conversion rate and tar yield were explored. The results indicated that the addition of methane/model biogas during biomass steam gasification could increase the H₂/CO ratio to about 2. Methane/model biogas, steam and Ni/γ-Al₂O₃ catalyst significantly affected the quality of syngas. High H₂ content syngas with H₂/CO ratio of about 2, biomass carbon conversion >85% and low tar yield was achieved under the optimum condition: S/C = 1.5, α = 0.2 and using Ni/γ-Al₂O₃ catalyst. According to ANOVA, methane and catalyst were the key influencing factors of the H₂/CO ratio and syngas yield, and the tar yield mainly depended on the Ni/γ-Al₂O₃ catalyst. Biogas, as a more environmentally friendly material than methane, can also regulate the composition of syngas co-feeding with biomass.     

In-situ photochemical fabrication of transition metal-promoted amorphous molybdenum sulfide catalysts for enhanced photosensitized hydrogen evolution

Amorphous molybdenum sulfide catalysts (MoS_x) can efficiently catalyze the H₂ evolution reaction (HER); however, their catalytic activities are still limited that need to be improved. Herein, transition metal-promoted MoS_x H₂ evolution catalysts were facilely fabricated through an in-situ photochemical reduction with inexpensive organic dye as photosensitizers. Under visible light (λ ≥ 420 nm), the promotional effect of transition metals on the H₂ evolution over MoS_x follows the order of Co > Fe ≈ Ni > unpromoted > Cu > Zn in Erythrosin B-triethanolamine (ErB-TEOA) system. The most active Co-promoted MoS_x (Co-MoS_x) catalyst is amorphous and composed of inter-connected nanoparticles with diameters of 30–50 nm. The Co-MoS_x catalyst contains both CoMoS phase and Co oxides/hydroxides. At the optimal reaction conditions, the Co-MoS_x catalyst with Co:Mo ratio of 4:6 exhibits enhanced H₂ evolution activity by 2 times as compared to unpromoted MoS_x and turnover numbers (TONs) of 30 and 60 based on ErB and catalyst used, respectively. The Co-MoS_x catalyst also shows a long-term stability without noticeable activity degradation. The formation pathways of Co-MoS_x catalyst and the photocatalytic mechanism for enhanced H₂ evolution performance were studied and a two-step reaction mechanism involved an oxidative quenching pathway of dye was proposed. This study demonstrates that in-situ concurrent photochemical fabrication with transition metal modification of amorphous MoS_x catalyst is an effective strategy for development of MoS_x-based HER catalysts with enhanced performances.     

Kinetic study of the catalytic reforming of biomass pyrolysis volatiles over a commercial Ni/Al2O3 catalyst

An original kinetic model has been proposed for the reforming of the volatiles derived from biomass fast pyrolysis over a commercial Ni/Al₂O₃ catalyst. The pyrolysis-reforming strategy consists of two in-line steps. The pyrolysis step is performed in a conical spouted bed reactor (CSBR) at 500 °C, and the catalytic steam reforming of the volatiles has been carried out in-line in a fluidized bed reactor. The reforming conditions are as follows: 600, 650 and 700 °C; catalyst mass, 0, 1.6, 3.1, 6.3, 9.4 and 12.5 g; steam/biomass ratio, 4, and; time on stream, up to 120 min. The integration of the kinetic equations has been carried out using a code developed in Matlab. The reaction scheme takes into account the individual steps of steam reforming of bio-oil oxygenated compounds, CH₄ and C₂-C₄ hydrocarbons, and the WGS reaction. Moreover, a kinetic equation for deactivation has been derived, in which the bio-oil oxygenated compounds have been considered as the main coke precursors. The kinetic model allows quantifying the effect reforming conditions (temperature, catalyst mass and time on stream) have on product distribution.     

Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst

Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H₂ yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H₂-TPD and the N₂ adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.     

Renewable hydrogen production by steam reforming of butanol over multiwalled carbon nanotube-supported catalysts

The conversion of bio-oxygenates into hydrogen (H₂) via catalytic steam reforming is a green approach for H₂ generation. In the present work, butanol was chosen as renewable feedstock for producing H₂. Two catalysts supported on multiwalled carbon nanotubes, Ni/CNT and Co/CNT, were synthesized by the wetness impregnation method and used for butanol reforming. Trials were performed in a fixed-bed reactor in the 623–773 K range using S/C ratio equal to 33.3 mol/mol (here, S/C denotes steam to carbon ratio). The Ni/CNT catalyst exhibited higher reforming activity. The best catalytic performance for Ni/CNT was observed at T = 773 K. At this temperature, high values of butanol conversion (87.3%) and H₂ yield (0.75 mol/mol) were observed at W/F_A0 = 16.7 g h/mol (here, W is the catalyst mass and F_A0 is the molar flow rate of butanol at the inlet). The performance of Ni/CNT catalyst for steam reforming of synthetic bio-butanol was also investigated at T = 773 K and H₂ yield of 0.65 mol/mol was achieved.     

Experimental investigation of ignition and combustion characteristics of single coal and biomass particles in O2/N2 and O2/H2O

Oxy-steam combustion is a potential new-generation option for CO₂ capture and storage. The ignition and combustion characteristics of single coal and biomass particles were investigated in a flow tube reactor in O₂/N₂ and O₂/H₂O at various oxygen concentrations. The ignition and combustion processes were recorded using a CCD camera, and the two-color pyrometry was used to estimate the volatile flame temperature and char combustion temperature. In O₂/N₂ and O₂/H₂O, coal ignites heterogeneously at <O₂> = 21–50%. In O₂/N₂, biomass ignites homogeneously at <O₂> = 21–30%, while it ignites heterogeneously at <O₂> = 40–50%. In O₂/H₂O, biomass ignites homogeneously at <O₂> = 21–50%. With increasing oxygen concentration, the ignition delay time, volatile burnout time and char burnout time are decreased, and the volatile flame temperature and char combustion temperature are increased. At a certain oxygen concentration in both atmospheres, the ignition delay time, volatile burnout time and char burnout time of biomass are shorter than those of coal. Moreover, biomass has a higher volatile flame temperature but a lower char combustion temperature than coal. The ignition delay time, volatile burnout time and char burnout time in O₂/H₂O are lower than those in O₂/N₂ for coal and biomass. The presence of H₂O can improve the combustion rates of coal and biomass. The volatile flame shows a lower temperature in O₂/H₂O than in O₂/N₂ at <O₂> = 21–50%. The char combustion shows a lower temperature in O₂/H₂O than in O₂/N₂ at <O₂> = 21–30%, while this behavior is switched at <O₂> = 40–50%. The results contribute to the understanding of the ignition and combustion characteristics of coal and biomass in oxy-steam combustion.     

High jolt-resistance monolithic CuO–CeO2/AlOOH/Al-fiber catalyst for CO-PROX: Influence of AlOOH/Al-fiber calcination on Cu–Ce interaction

Micro-reactors for the preferential oxidation of CO in H₂-rich stream (CO-PROX) are attractive for PEMFCs employed in portable electronic devices and automobiles, but the jolt is inevitable, which makes micro-reactors necessitate high jolt resistance. The monolithic structured catalyst could effectively resolve these problems. Herein, we employed the thin-felt monolithic Al-fiber substrate to fabricate the CuO–CeO₂/AlOOH/Al-fiber catalyst for the CO-PROX reaction. This catalyst was prepared via first growing AlOOH nanosheets onto the Al-fiber surface by steam oxidation method, followed by depositing CuO–CeO₂ onto the AlOOH/Al-fiber support. The preferred catalyst delivered 100% CO conversion and 81% O₂ selectivity at 140 °C with a gas hourly space velocity of 12,000 mL g^?1 h^?1, and particularly, performed stably for 120 h at the changeable temperatures of 120–160 °C. This work provides a strategy to tailor a qualified monolithic catalyst that couples the promising jolt resistance and catalytic performance at 120–160 °C.     

Syngas production by steam and oxy-steam reforming of biogas on monolith-supported CeO2-based catalysts

In this study, the syngas production by steam reforming (SR) and oxy-steam reforming (OSR) of clean biogas over cordierite monoliths (400 cpsi) lined with Ni, Rh, or Pt on CeO₂ catalyst was deeply investigated. Structured catalysts were prepared by using an alternative method to traditional washcoating based on the combination of the solution combustion synthesis (SCS) with the wetness impregnation (WI) technique. TEM and SEM analysis were used to study the morphology of the catalytic layer and to determine its thickness, while the quality of the coating in terms of adhesion on the monolith was evaluated by ultrasonic treatment in isopropyl alcohol solution. The performance and the stability of the structured catalysts were investigated at different process parameters, namely temperature (700–900 °C), steam-to-carbon (S/C = 1–5) and oxygen-to-carbon (O/C = 0.1–0.2) molar ratios, and weight space velocity (WSV = 30,000–250,000 NmL g_cat^?1 h^?1). The SCS + WI deposition method allowed obtaining a uniform and thin coated layer with high mechanical strength. The following order of activity was exploited: Rh > Pt > Ni for biogas SR and Rh > Pt ≈ Ni for biogas OSR. The Rh-based catalyst exhibited higher activity and long-lasting stability towards biogas SR and OSR reactions for syngas production.     

Tailoring Cu/Al2O3 catalysts for the catalytic pyrolysis of tomato waste

In this study, pyrolysis of tomato waste has been performed in fixed bed tubular reactor at 500 °C, both in absence and presence of Cu/Al₂O₃ catalyst. The influences of heating rate, catalyst preparation method and catalyst loading on bio-oil yields and properties were examined. According to pyrolysis experiments, the highest bio-oil yield was obtained as 30.31% with a heating rate of 100 °C/min, 5% Cu/Al₂O₃ catalyst loading ratio and co-precipitation method. Results showed that the catalysts have strong positive effect on bio-oil yields. Bio-oil quality obtained from fast catalytic pyrolysis was more favorable than that obtained from non-catalytic and slow catalytic pyrolysis.     

Hydrogen production from oil sludge gasification/biomass mixtures and potential use in hydrotreatment processes

Gasification of oil sludge (OS) from crude oil refinery and biomass was investigated to evaluate hydrogen production and its potential use in diesel oil hydrodesulphurization process. Gasification process was studied by Aspen Hysys^® tools, considering different kinetic model for main OS compounds. Air and superheated steam mixtures as gasifying agents were simulated. Gasification parameters like: temperature, syngas chemical composition and gas yield were evaluated. Results showed OS thermal conversion needs a working temperature above 1300 °C to ensure a high conversion (>90%) of OS compounds. Thermal energy requirement for gasification was estimated between 0.80 and 1.25 kWh/kg OS, considering equivalence air (ER) and steam/oil sludge (SOS) ratio between 0.25-0.37 and 0.2–1.5 kg steam/kg OS, respectively. The gas yield was 2.28 Nm³/kg OS, with a H₂ content close to 25 mol%, for a H₂ potential production about 1.84 Nm³ H₂/kg OS; nevertheless, when OS and biomass mixtures are used, hydrogen production increases to 3.51 Nm³ H₂/kg OS, meaning 37% of H₂ (from natural gas) required for diesel oil hydrodesulphurization could be replaced, becoming an added value technological alternative for OS waste conversion as a source of H₂, inducing a considerable reduction of greenhouse gases and non-renewables resources.     

Comprehensive experimental study on supercritical water gasification of oilfield sludge: Effect of operation parameters,and catalysts on the products

Supercritical water gasification (SCWG) was adopted to treat oilfield sludge and produce syngas. The effect of temperature (400–450 °C), reaction time (30–90 min) and catalyst addition on syngas production and residual products during SCWG of oilfield sludge was studied. When increasing SCWG temperature from 400 to 450 °C with reaction time of 60 min, the H₂ yield and the selectivity of H₂ increased significantly from 0.53 mol/kg and 75.53% to 0.98 mol/kg and 78.09%, respectively. It is noteworthy that when the reaction time was too long, CO₂ and CO were converted to CH₄ with the consumption of H₂ via methanation reaction. The addition of Ni/Al₂O₃ catalyst can substantially promote the production of high-quality syngas from SCWG of oilfield sludge. The H₂ yield and its selectivity at 450 °C and 60 min were as high as 1.37 mol/kg and 84.05% with 10Ni/Al catalyst. Moreover, the catalysts with bimetal loading (Fe–Ni, Rb–Ni or Ce–Ni) were found to be beneficial for improving gasification efficiency, H₂ yield, and the degradation of organic compounds. Among them, 5 wt% Rb on 10Ni/Al catalyst performed the best catalytic activity for SCWG at 450 °C and 60 min, which had the highest H₂ yield of 1.67 mol/kg and selectivity of 86.09%. More than 90% of total organic carbon in sludge was decomposed after the SCWG with all the catalysts. These findings indicated that catalytic SCWG is a promising alternative for efficiently dealing with oilfield sludge.     

Hydrogen production with a low carbon monoxide content via methanol steam reforming over CuxCeyMgz/Al2O3 catalysts: Optimization and stability

Catalytic activities of Ce–Mg promoted Cu/Al₂O₃ catalysts via methanol steam reforming was investigated in terms of the methanol conversion level, carbon monoxide selectivity and hydrogen yield. The factors chosen were the reaction temperature, copper content, Mg/(Ce + Mg) weight-percentage and steam to carbon ratios. The catalysts were prepared by co-precipitation and characterized by means of XRD, BET, H₂-TPR, and FESEM. The Ce–Mg bi-promoter catalysts gave higher performance due to magnesium penetration into the cerium structure causing oxygen vacancy defects on the ceria. A response-surface-model was then designed to optimize the condition at a 95% confidence interval for complete methanol conversion to a high H₂ yield with a low CO content, and revealed an optimal copper level of 46–50 wt%, Mg/(Ce + Mg) of 16.2–18.0%, temperature of 245–250 °C and S/C ratio of 1.74–1.80. No deactivation of the Cu_0.5Ce_0.25Mg_0.05/Al catalyst was observed during a 72-h stability test.     

The kinetics of acetic acid steam reforming on Ni/Ca-Al2O3 catalyst

As a significant by-product of many thermochemical and biological waste conversion processes, acetic acid (AcOH) is often investigated as model feedstock in the production of sustainable hydrogen from non-fossil sources. The kinetics of its steam reforming were extracted from packed bed reactor experiments over an industrially produced 14 wt% Ni/Ca-Al₂O₃ catalyst at atmospheric pressure. The model consisting of AcOH steam reforming producing CO₂ and H₂, AcOH decomposition to CO and H₂, and water gas shift, achieved the best fit, reflected in the lowest average relative errors (ARE) with experimental results, with ARE values below 5.4% and 6.4% on AcOH and water conversions respectively, and below 4% on H₂ mol fraction. This model was validated away from equilibrium using additional experimental points, as well as for a wide range of equilibrium conditions with varying temperature (600–700 °C) and feed molar steam to carbon ratios (3–8) at atmospheric pressure using an independent method.     

Carbon deposition on Ni/ZrO2–CeO2 catalyst during steam reforming of acetic acid

Steam reforming of acetic acid, one model compounds of bio-oil, was studied on the Ni/ZrO₂–CeO₂ catalysts which were prepared by the impregnation method. The results showed that high acetic acid conversion and hydrogen yield were obtained in the temperature range of 650–750 °C when H₂O/HAC ratio was 3. Nevertheless, the catalyst deactivation was caused by carbon deposition eventually with time-on-stream. In order to discuss the behavior of the carbon deposition on the Ni/ZrO₂–CeO₂ catalyst during steam reforming of bio-oil, the structure and morphology of carbon deposition were investigated by BET, XRD, TG/DTA, TPR, SEM and EDX techniques. All the experimental results showed acetone and CO were the important carbon precursors of acetic acid reforming and the graphitic-like carbon was the main type of carbon deposition on the surface of the deactivated 12%Ni/CeO₂–ZrO₂ catalyst.