Catalytic steam reforming of acetic acid for hydrogen production

A variety of supported metal catalysts were tested under conditions of steam reforming of acetic acid (HAc), which was selected as a model compound for pyrolysis oil. The influence of several parameters on catalytic activity and selectivity were examined, including catalyst composition, i.e. nature of the metal and the carrier, reaction temperature and time on stream. The metallic phase of such catalysts was comprised of various metals, such as Pt, Pd, Rh, Ru and Ni, which were supported on metal oxides carriers, such as _Al2O3${\mathrm{Al}}_2{\mathrm{O}}_3$, _La2O3/_Al2O3${\mathrm{La}}_2{\mathrm{O}}_3/{\mathrm{Al}}_2{\mathrm{O}}_3$, MgO/_Al2O3$\mathrm{MgO}/{\mathrm{Al}}_2{\mathrm{O}}_3$ and _CeO2/_Al2O3${\mathrm{CeO}}_2/{\mathrm{Al}}_2{\mathrm{O}}_3$. It was found that Ni-based and Ru-based catalysts present high activity and selectivity toward hydrogen production. Ru catalysts supported on _La2O3/_Al2O3${\mathrm{La}}_2{\mathrm{O}}_3/{\mathrm{Al}}_2{\mathrm{O}}_3$ and MgO/_Al2O3$\mathrm{MgO}/{\mathrm{Al}}_2{\mathrm{O}}_3$ carriers, showed good long-term stability as a function of time on stream. However, Ni catalysts were not as stable as Ru catalysts. The amount of carbon deposited on each catalyst was estimated, and it was found that it depends strongly on the nature of the catalyst.     

Nickel catalyst auto-reduction during steam reforming of bio-oil model compound acetic acid

Transition metal catalysts widely used in refineries are provided as oxides and require pre-reduction to become activated. The auto-reduction of a NiO/Al₂O₃ catalyst with acetic acid (HAc) followed by HAc steam reforming was investigated in a packed bed reactor. Effects of temperature and molar steam to carbon ratio (S/C) on reduction kinetics and catalyst performance were analysed. Results showed that a steady steam reforming regime along with complete NiO reduction could be obtained after a coexistence stage of reduction and reforming. A 2D nucleation and nuclei growth model fitted the NiO auto-reduction. The maximum reduction rate constant was attained at S/C = 2. Steam reforming activity of the auto-reduced catalyst was just below that of the H₂-reduced catalyst, probably attributed to denser carbon filament formation and larger loss of active Ni. Despite this, a H₂ yield of 76.4% of the equilibrium value and HAc conversion of 88.97% were achieved at 750 °C and S/C = 3.     

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.     

Hydrogen production from acetic acid steam reforming over Ti-modified Ni/Attapulgite catalysts

Steam reforming of bio-oil derived oxygenates is a green and sustainable method for hydrogen production. In this work, hydrogen production from steam reforming of acetic acid (SRAA) was investigated over Ti-modified Ni/Attapulgite (ATP) catalysts that prepared via sequential precipitation technique. The effects of Ti additive, precipitation sequence and Ti-salt precursors (TiCl₄, TiOSO₄) on the structural and physicochemical properties of catalysts were characterized by N₂ adsorption-desorption, XRD, FT-IR, HRTEM, XPS, H₂-TPR and NH₃-TPD. These results indicated that the interaction among Ti species, Ni active metal and ATP enhanced the reduction performance as well as weakened surface acidity of the Ni/ATP catalyst, and also promoted the electron transfer to form Ni^δ? species. Obviously, compared with Ti precursor salts, the precipitation sequences played a key role in determining the surface properties of Ti-modified catalysts. Among them, the Ni–Ti_S/ATP catalyst synthesized by co-precipitation method exhibited better reducibility and lower surface acidity, as well as produced more Ni^δ? species and Ni^δ?-O_v-Ti³⁺ interface sites. Then the synergistic effects among the above-mentioned characters made the Ni–Ti_S/ATP catalyst present highest carbon conversion (93.4%) and H₂ yield (77.6%) during SRAA reactions. The analyses of XRD, HRTEM and TG were implemented on used catalysts and discovered Ni–Ti_S/ATP catalysts shown promising metal sintering and coke resistance, which mainly caused by the presence of flat Ni–Ti@ATP structures. The possible conversion mechanism of acetic acid in the flat Ni–Ti@ATP structure of co-precipitation Ti-modified catalyst was also elucidated.     

A CFD approach on simulation of hydrogen production from steam reforming of glycerol in a fluidized bed reactor

Hydrogen production from steam reforming of glycerol in a fluidized bed reactor has been simulated using a CFD method by an additional transport equation with a kinetic term. The Eulerian–Eulerian two-fluid approach was adopted to simulate hydrodynamics of fluidization, and chemical reactions were modelled by laminar finite-rate model. The bed expansion and pressure drop were predicted for different inlet gas velocities. The results showed that the flow system exhibited a more heterogeneous structure, and the core-annulus structure of gas–solid flow led to back-mixing and internal circulation behaviour, and thus gave a poor velocity distribution. This suggests the bed should be agitated to maintain satisfactory fluidizing conditions. Glycerol conversion and H₂ production were decreased with increasing inlet gas velocity. The increase in the value of steam to carbon molar ratio increases the conversion of glycerol and H₂ selectivity. H₂ concentrations in the bed were uneven and increased downstream and high concentrations of H₂ production were also found on walls. The model demonstrated a relationship between hydrodynamics and hydrogen production, implying that the residence time and steam to carbon molar ratio are important parameters. The CFD simulation will provide helpful data to design and operate a bench scale catalytic fluidized bed reactor.     

Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers

This work presents the experimental results obtained during auto-thermal chemical-looping reforming (CLR) in a 900 W_th circulating fluidized bed reactor under continuous operation using methane as fuel. Two oxygen carriers based on NiO and supported on γ-Al₂O₃ and α-Al₂O₃ were used during more than 50 h of operation with each oxygen carrier. During operation the effect of different operating variables, like fuel reactor temperature, H₂O/CH₄ molar ratio and solid circulation rate, on CH₄ conversion and gas product distribution was analyzed. It was found that in all operating conditions CH₄ conversion was very high (>98%) and the most important variable affecting to the gas product distribution was the solid circulation rate, that is, NiO/CH₄ molar ratio. Similar gas product distribution was obtained working with both oxygen carriers although at different NiO/CH₄ molar ratios. The oxygen carrier of NiO on α-Al₂O₃ needed lower NiO/CH₄ molar ratio to reach the same gas product composition than the oxygen carrier of NiO on γ-Al₂O₃. Working at optimal operating conditions, 2.5 moles of H₂ per mol of CH₄ could be obtained in this process.During operation the oxygen carrier particles maintained their physical and chemical properties. These results suggest that these oxygen carriers could have a high durability, being suitable oxygen carriers for a CLR system.     

Steam reforming of heptane in a fluidized bed membrane reactor

n-Heptane served as a model compound to study steam reforming of naphtha as an alternative feedstock to natural gas for production of pure hydrogen in a fluidized bed membrane reactor. Selective removal of hydrogen using Pd₇₇Ag₂₃ membrane panels shifted the equilibrium-limited reactions to greater conversion of the hydrocarbons and lower yields of methane, an intermediate product. Experiments were conducted with no membranes, with one membrane panel, and with six panels along the height of the reactor to understand the performance improvement due to hydrogen removal in a reactor where catalyst particles were fluidized. Results indicate that a fluidized bed membrane reactor (FBMR) can provide a compact reformer for pure hydrogen production from a liquid hydrocarbon feedstock at moderate temperatures (475-550 °C). Under the experimental conditions investigated, the maximum achieved yield of pure hydrogen was 14.7 moles of pure hydrogen per mole of heptane fed.     

Experiments on hydrogen production from methanol steam reforming in fluidized bed reactor

A novel approach for the hydrogen production which integrated methanol steam reforming and fluidized bed reactor (FBR) was proposed. The reaction was carried out over Cu/ZnO/Al₂O₃ catalysts. The critical fluidized velocities under different catalyst particle sizes and masses were obtained. The influences of the operating parameters, including that of H₂O-to-CH₃OH molar ratio, feed flow rate, reaction temperature, and catalyst mass on the performance of methanol steam reforming were investigated in FBR to obtain the optimum experimental conditions. More uniform temperature distribution, larger surface volume ratio and longer contacting time can be achieved in FBR than that in fixed bed reactor. The results indicate that the methanol conversion rate in FBR can be as high as 91.95% while the reaction temperatures is 330 °C, steam-to-carbon molar ratio is 1.3, and feed flow rate is 540 ml/h under the present experiments, which is much higher than that in the fixed bed.     

Hydrogen from aqueous fraction of biomass pyrolysis liquids by catalytic steam reforming in fluidized bed

Sustainable pathways for producing hydrogen as a synthesis intermediate or as a clean energetic vector will be needed in the future. Renewable biomass resources should be taken into account in this new scenario. Processing through a pyrolysis step, optimized to high liquid production (bio-oil), increases the energy bulk density of biomass for transportation. Steam reforming of the aqueous fraction is an alternative process that increases the hydrogen content of the syngas. However, the thermochemical conversion of organic compounds derived from biomass involves drawbacks such as coke formation on the catalysts. This work studies the performance of Ni-Al catalysts modified with Ca or Mg in the steam reforming of the aqueous fraction of pyrolysis liquids and the resulting coke deposits. The catalyst composition influenced the quantity and type of coke deposits. Calcium improved the formation of carbonaceous products leading to lower H₂/CO ratios while magnesium improved the WGS (water gas shift) reaction. The strategy of reducing the space velocity resulted in a low coke removal although the addition of small quantities of oxygen decreased the coke content of the catalyst by more than 50% weight. Greater efficiency and further catalyst development are needed to improve the energetic requirements of the process.     

Steam reforming of propane in a fluidized bed membrane reactor for hydrogen production

Steam reforming of propane was carried out in a fluidized bed membrane reactor to investigate a feedstock other than natural gas for production of pure hydrogen. Close to equilibrium conditions were achieved inside the reactor with fluidized catalyst due to the very fast steam reforming reactions. Use of hydrogen permselective Pd₇₇Ag₂₃ membrane panels to extract pure hydrogen shifted the reaction towards complete conversion of the hydrocarbons, including methane, the key intermediate product. Irreversible propane steam reforming is limited by the reversibility of the steam reforming of this methane. To assess the performance improvement due to pure hydrogen withdrawal, experiments were conducted with one and six membrane panels installed along the height of the reactor. The results indicate that a compact reformer can be achieved for pure hydrogen production for a light hydrocarbon feedstock like propane, at moderate operating temperatures of 475–550 °C, with increased hydrogen yield.     

Enhancement of membrane hydrogen separation on glycerol steam reforming in a fluidized bed reactor

Membrane hydrogen separation can effectively promote fuel conversion and hydrogen yield by means of altering chemical equilibrium of reforming reactions. In this work, the enhancing process of glycerol steam reforming via a fluidized bed membrane reactor is numerically investigated. Under the framework of the Euler-Euler method, chemical kinetic model is implemented and the reforming performance with and without membrane separation is compared. The effect of densified zones caused by membrane separation is examined. Meanwhile, the impacts of operating parameters including hydrogen partial pressure on the permeate side and fuel gas velocity on densified zones and hydrogen yield are evaluated. The results demonstrate that the excessive reduction of hydrogen partial pressure on the permeate side and the increase of feed gas velocity are detrimental to fuel conversion and hydrogen yield.     

Hydrogen production from acetic acid steam reforming over nickel-based catalyst synthesized via MOF process

In our earlier work, we have reported that Ni supported on γ-Al₂O₃–La₂O₃–CeO₂ (ALC) catalyst prepared via metal organic framework (MOF) was more active for acetic acid steam reforming (AASR) [1]. Here we report detailed study on the performance of this catalyst for AASR. Effects of operating conditions such as temperatures (400–650 °C), steam to carbon molar ratio (S/C) and feed flow rate (1.5–5.5 mL/h) were evaluated and optimized. Results showed an excellent activity for AASR at the molar ratio S/C = 6.5, feed flow rate = 2.5 mL/h and, at 600 °C with almost total conversion and more than 90% of H₂ yield. The ordered porous structure of embedded nickel supported catalyst promotes excellent steam reforming activity and water gas shift reaction even at low temperatures, which leads to the good stable behaviour up to 36 h of TOS. The coke formation was also significantly suppressed by ALC support. Catalyst regenerated by passing oxygen at 500 °C and followed by reduction in hydrogen also show a good activity. Catalysts were characterized by DT-TGA, XRD, TEM, H₂-TPR and N₂-adsorption-desorption to understand the micro structure and coke deposition behaviour.     

Chemical looping dry reforming of benzene as a gasification tar model compound with Ni- and Fe-based oxygen carriers in a fluidized bed reactor

Gasification tar during a fluidized bed operation impedes syngas utilization in downstream applications. Among tar constituents sampled during biomass gasification, benzene was the most abundant species. Thus, benzene was used as a model compound for chemical looping dry reforming (CLDR) over iron (Fe) and nickel (Ni) metals impregnated on silicon carbide (SiC) in a lab-scale fluidized bed reactor to convert it into hydrogen and carbon monoxide (H₂ and CO). A high benzene conversion rate (>90%) was observed at a higher experimental temperature (above 730 °C). Catalytic conversion of benzene using NiFe/SiC catalyst resulted in higher H₂ production whereas higher levels of CO were produced with Fe/SiC catalyst at an elevated temperature. Control experiments using an empty bed and SiC bed showed the formation of both the biphenyls and excessive carbon deposits. Air oxidation was also performed for the regeneration of oxygen carrier during the chemical looping operation.     

Hydrogen production by steam reforming of acetic acid: Comparison of conventional supported metal catalysts and metal-incorporated mesoporous smectite-like catalysts

The activities of various metal catalysts were tested in steam reforming of acetic acid for the production of H₂, using conventional metal oxides and transition metal-incorporated mesoporous smectite-like materials as supports. It has been found that Pt is superior to Ni, Co, and Fe among Al₂O₃ supported catalysts, Al₂O₃ is more effective than ZrO₂ and SiO₂ as support for Pt, Ni incorporated smectite (SM(Ni)) support is more effective than Fe and Co incorporated ones for Pt, and SM(Ni) is also active in the absence of Pt. The total activity for the conversion of acetic acid is in the order of Pt/Al₂O₃ > Pt/SM(Ni) > SM(Ni) but the ability of H₂ production is comparable among these catalysts. These catalysts (and the other ones) were observed to lose their activities during the reforming reactions. The activity of Pt/Al₂O₃ decreased during the whole course of reaction up to 10 h. In contrast, the activity of SM(Ni) also decreased within 2 h but it showed a stable activity in the following stage of reaction. The initial activity of the used Pt/SM(Ni) and SM(Ni) was able to be almost completely restored by thermal treatment with H₂ but less effectively for the used Pt/Al₂O₃. The catalyst deactivation was shown to occur by the formation and deposition of carbon materials on the catalysts (XRD, TEM, thermal analysis). The properties of carbon deposits formed on Pt/Al₂O₃ and SM(Ni) catalysts should be different and this may be responsible for the differences in the extent of deactivation and in the regeneration behavior between the two catalysts.     

Catalytic steam reforming of bio-oil

Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process and the influence of operating conditions will be presented along with the catalysts and processes investigated in the literature.     

Production of hydrogen via steam reforming of acetic acid over Ni and Co supported on La2O3 catalyst

Nickel (Ni)-cobalt (Co) supported on lanthanum (III) oxide (La₂O₃) catalyst was prepared via impregnation technique to study the steam reformation of acetic acid for hydrogen generation by using one-step fixed bed reactor. Moreover, in order to specify the physical and the chemical attributes of the catalyst, X-ray diffraction (XRD), nitrogen physisorption, temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia and carbon dioxide (TPD-NH₃ and CO₂), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) methods were employed. The nitrogen physisorption analysis showed that the presence of Co on Ni/La₂O₃ improved the textural properties of the catalyst by increasing the surface area, the pore diameter and the pore volume of the catalyst. This improved the dispersion of metal particle and caused a reduction in the size of metal particle, and consequently, increased the catalytic activity, as well as the resistance to coke formation. On top of that, the condensation and the dehydration reactions during acetic acid steam reforming created carbon deposition on acidic site of the catalyst, which resulted in the deactivation of catalyst and the formation of coke. Besides, in this study, Ni/La₂O₃ contributed to a high acetic acid conversion (100%) at 700 °C, but it produced more coking compared to Ni–Co/La₂O₃ and Co/La₂O₃ catalysts.     

Effect of ceria addition on NiRu/CeO2Al2O3 catalysts in steam reforming of acetic acid

NiRu bimetallic catalysts with different amount of CeO₂ loaded on the γ-Al₂O₃ support were prepared. The properties of catalysts were characterized by means of N₂ adsorption-desorption, XRD, H₂-TPR and XPS techniques. Catalytic activities for the steam reforming of acetic acid over these catalysts were investigated at the temperature range from 650 °C to 750 °C. The addition of CeO₂ dramatically improved the activity and stability of the catalyst. Among these catalysts, the NiRu/10CeAl catalyst showed the highest catalytic activity as well as a good stability owing to the abundant Ce³⁺ on the surface of catalyst. The existence of Ce³⁺ promoted the formation of CO₂ from CO because of the mobilizable oxygen, which was favorable for the formation of hydrogen. The coke amount and species deposited on the catalysts after the activity tests were analyzed by DTG. As expected, the NiRu/10CeAl catalyst showed the best resistance to carbon formation. The temperature stepwise steam decoking experiment of the spent catalysts was conducted to elucidate the relationship between the existence of Ce³⁺ and the decoking abilities of various catalysts. It was verified that the existence of Ce³⁺ significantly promoted the decoking abilities of the catalysts.     

Effect of W incorporation on the product distribution in steam reforming of bio-oil derived acetic acid over Ni based Zr-SBA-15 catalyst

Zirconia incorporated SBA-15 type mesoporous material was synthesized following a one-pot hydrothermal route, characterized and used as the catalyst support in the synthesis of Ni and bi-metallic Ni–W based catalysts. Performances of these catalysts were tested in steam reforming of AcOH. Catalytic activity tests proved that the performances of SBA-15 and Zr-SBA-15 supported Ni based catalysts were highly stable and they also showed very high activity in steam reforming of acetic acid, giving complete conversion at temperatures over 700 °C. Product distributions were shown to be strongly influenced by the composition of the catalyst. In the case of 5Ni@Zr-SBA-15, syngas produced at 750 °C contained about 54% H₂, 22% CO, 20% CO₂ and 4% CH₄. These results indicated that decarboxylation reaction of AcOH to CH₄ and CO₂ was minimized over this catalyst. Results were considered to be highly promising for the production of hydrogen rich syngas. It was most interesting to observe that modification of this catalyst by the addition of tungsten caused significant changes in the product distribution. For instance, syngas produced over 5Ni-50W@Zr-SBA-15 at the same reaction conditions, contained equimolar quantities of H₂ and CO (about 47.5% each) with very small amounts of CO₂ and CH₄ (about 3% and 2%, respectively). Production of a syngas with such a composition was considered to be highly attractive from the point of view of a resource gas for dimethyl ether and Fischer-Tropsch synthesis.     

Ceria-promoted Ni@Al2O3 core-shell catalyst for steam reforming of acetic acid with enhanced activity and coke resistance

A series of Ni@Al₂O₃ core-shell catalysts with ceria added to the surface of Ni nanoparticles or inside the alumina shell were prepared, and the effect of ceria addition on the performance of the catalyst in the steam reforming of acetic acid was investigated. The prepared catalysts were characterized by BET, XRD, HRTEM, H₂-TPR and DTG. The addition of ceria to the surface of nickel nanoparticles greatly enhanced the activity of catalyst owing to the presence of the mobile oxygen, which migrated from the ceria lattice. Among the prepared catalysts, the Ni@Al10Ce catalyst showed the highest activity with a conversion of acetic acid up to 97.0% even at a low temperature (650 °C). The molar ratio of CO₂/CO was also improved due to the oxidation of CO by the mobile oxygen into CO₂. The coke formation on the core-shell catalysts was significantly inhibited by the addition of ceria to the surface of nickel nanoparticles due to the oxidation of carbon species by the mobile oxygen in the ceria lattice. However, the Ni@Al10Ce-a catalyst with ceria added to the alumina shell showed a low activity and the formation of a large amount of coke. It is suggested that only the ceria in close to the Ni surface has the promoting effect on the catalytic performance of the Ni@Al₂O₃ catalyst in the steam reforming of acetic acid.