Catalytic performance of steam reforming of ethanol at low temperature over LaNiO3 perovskite

A LaNiO₃ perovskite catalyst was prepared using the coprecipitation–oxidation hydrothermal method, followed by calcination at 600 °C for 2 h. The as-prepared sample was composed of La(OH)₃ in nanorod structures and was covered with poorly crystalline Ni(OH)₂. The mixed metal hydroxides were converted into cubic LaNiO₃ perovskite after calcination at 600 °C. A catalytic steam reforming of ethanol (SRE) reaction for hydrogen production was performed in a fixed-bed reactor. The catalyst was reduced in situ in hydrogen at 400 °C prior to the reaction. The ethanol conversion reached 100% at 300 °C with 70% hydrogen selectivity. The highly catalytic activity of the reduced catalyst was due to the well-dispersion of Ni particles on the surface of active catalyst was formed in the in situ reduced catalyst. After a 80 h time-on-stream test at 350 °C, the used catalyst presented a La₂O₂CO₃ component that was formed owing to the reaction of the CO₂ product with La₂O₃. La₂O₂CO₃ acted as a carbon reservoir to eliminate the deposited carbon and further stabilized the Ni particles on the La₂O₃ surface, which resulted in the highly catalytic activity during the entire reaction period. The deposited carbon after the SRE reaction was further examined by TGA, TPR, elemental analysis, and TEM.     

Hydrogen production via steam reforming of methanol over Cu/(Ce,Gd)O2−x catalysts

Hydrogen production via steam reforming of methanol is carried out over Cu/(Ce,Gd)O_2−x catalysts at 210–600 °C. The CO content in reformate is about 1% at 210–270 °C, which are the typical temperature for hydrogen production via steam reforming of methanol. Largest H₂ yield and CO₂ selectivity and smallest CO content are obtained at 240 °C. The formation rate of CO increases with increasing temperature. The average formation rate of CO becomes larger than that of CO₂ at about 450 °C. The H₂ yield, the CO₂ selectivity and the CO content become constant at about 550 °C. At 240 °C, the smallest CO content is obtained with a catalyst weight of 0.5 g and a Cu content of 3 wt%. The H₂ yield, defined as H₂/(CO + CO₂) in formation rates, at 240 °C is always 3 and not affected by the variations of either the catalyst weight or the Cu content.     

Effect of Ce on the structural features and catalytic properties of La(0.9−x)CexFeO3 perovskite-like catalysts for the high temperature water-gas shift reaction

La_(0.9−x)Ce_xFeO₃ perovskite-like catalysts were investigated for the production of hydrogen from simulated coal-derived syngas via the water-gas shift reaction in the temperature range 450-600 °C and at 1 atm. These catalysts exhibited higher activity at high temperatures (T ≥ 550 °C), compared to that of a commercial high temperature iron-chromium catalyst at 450 °C. Addition of a low Ce content (x = 0.2), has little influence on the formation of the LaFeO₃ perovskite structure, but enhances catalytic activity especially at high temperatures with 19.17% CO conversion at 550 °C and 40.37% CO conversion at 600 °C. The LaFeO₃ perovskite structure and CeO₂ redox properties play an important role in enhancing the water-gas shift activity. Addition of a high Ce content (x = 0.6) inhibits the formation of the LaFeO₃ perovskite structure and decreases catalyst activity.     

Continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production

In this study, the continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production by a simultaneous flow concept of catalyst and sorbent for reaction and regeneration using two moving-bed reactors has been evaluated experimentally. A Ni-based catalyst (NiO/NiAl₂O₄) and a lime sorbent (CaO) were used for glycerol steam reforming with and without in-situ CO₂ removal at 500 °C and 600 °C. The simultaneous regeneration of catalyst and sorbent was carried out with the mixture gas of N₂ and steam at 900 °C. The product gases were measured by a GC gas analyzer. It is obvious that the amounts of CO₂, CO and CH₄ were reduced in the sorption-enhanced steam reforming of glycerol, and the H₂ concentration is greatly increased in the pre-CO₂ breakthrough periods within 10 min both 500 °C and 600 °C. The extended time of operation for high-purity hydrogen production and CO₂ capture was obtained by the continuous sorption-enhanced steam reforming of glycerol. High-purity H₂ products of 93.9% and 96.1% were produced at 500 °C and 600 °C and very small amounts of CO₂, CH₄ and CO were formed. The decay in activity during the continuous reaction-regeneration of catalyst and sorbent was not observed.     

La0.6Sr0.4Co0.8Ni0.2O3−δ hollow fiber membrane reactor: Integrated oxygen separation – CO2 reforming of methane reaction for hydrogen production

An integrated reactor system which combines oxygen permeable La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ (LSCN) perovskite ceramic hollow fiber membrane with Ni based catalyst has been successfully developed to produce hydrogen through oxy-CO₂ reforming of methane (OCRM). Dense La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ hollow fiber membrane was prepared using phase inversion-sintering method. OCRM reaction was tested from 650 °C to 800 °C with a quartz reactor packed with 0.5 g Ni/Al₂O₃ catalyst around the LSCN hollow fiber membrane. CH₄ and CO₂ were used as reactants and air as the oxygen source was fed through the bore side of the hollow fiber membrane. In order to gauge the effectiveness of this membrane reactor system, air flow was closed at 800 °C and dry reforming of methane (DRM) was tested for comparison. The results show that the oxygen fluxes of LSCN membrane swept by helium are nearly 3 times less than those swept by OCRM reactants. With increasing temperature and oxygen supply, methane conversion in the OCRM reactor reaches 100%, but CO₂ conversion decreases from 87% to 72% due to the competition reaction with POM. CO selectivity is as high as nearly 100% at reaction temperatures of 700 °C–800 °C while H₂ selectivity reaches a maximum of 88% at 700 °C. At 800 °C, when air supply was closed and DRM was conducted for comparison, CO selectivity decreased to 91%, resulting in carbon deposition which was around 4 times more than those obtained under OCRM reaction and H₂/CO ratio decreased from 0.93 to 0.74, showing better carbon resistance and higher H₂ selectivity of the Ni-based catalyst over the integrated oxygen separation-OCRM reaction across the LSCN hollow fiber membrane reactor.     

Study on the preparation of Ni–La–Ce oxide catalyst for steam reforming of ethanol

Two schemes for design and preparation of Ni–La–Ce oxide catalysts for steam reforming of ethanol were proposed in this work. The one via citrate complexing method was designed as NiO supported on ceria-lanthanum oxide (CL) solid solution, in which the strong interaction between NiO and CL solid solution was beneficial to inhibit the aggregation of NiO particles, and the abundant of oxygen vacancies existed in CL solid solution was in favor of carbon elimination from catalyst surface. The other was schemed as LaNiO₃ with perovskite structure loaded on CeO₂ support by using impregnation method, in which the particles of metal Ni derived from reduction of LaNiO₃ were highly dispersed, and the formation of La₂O₂CO₃ in the reaction process could act as the carbon scavenger. Both of the catalysts exhibited very good performance for steam reforming of ethanol (SRE), complete C₂H₅OH conversion was obtained with 70.3% of H₂ selectivity at 400 °C over the catalyst obtained from former method and complete C₂H₅OH conversion was achieved at 450 °C with 67% of H₂ selectivity over the catalyst from latter method. The catalyst made according to the citrate complexing method was more active for SRE and more selective for H₂ production. Both of the catalysts displayed very good anti-sintering ability which was tested at 650 °C and at a high space velocity of 180,000 ml g_cat⁻¹ h⁻¹ with reaction mixture of H₂O/C₂H₅OH = 3 in mole ratio. The results indicated that both of oxygen vacancy and La₂O₂CO₃ possessed the ability to remove the deposited carbon, and compared with La₂O₂CO₃ the oxygen vacancy could reduce one third more of the carbon deposited according to TG tests.     

Steam reforming of iso-octane toward hydrogen production over mono- and bi-metallic Cu–Co/CeO2 catalysts: Structure-activity correlations

Τhe feasibility of tailoring the iso-octane steam reforming activity of Cu/CeO₂ catalysts through the use of Co as a second active metal (Cu_20−xCo_x, where x = 0, 5, 10, 15, 20 wt%), is investigated. Characterization studies, involving N₂ adsorption–desorption at −196 °C (BET), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and Temperature Programmed Reduction (H₂-TPR), were carried out to reveal the impact of the morphological, structural and surface properties of the catalysts on the reforming performance. The results showed that reforming activity was monotonically increased upon increasing cobalt loading. The Co/CeO₂ catalyst demonstrated the optimum performance with a H₂ yield of 70–80% in the 600–800 °C temperature interval. The Co/CeO₂ catalyst exhibited also excellent stability at temperatures above 700 °C, while Cu-based catalysts rapidly deactivated in long term stability tests. A close correlation between surface/redox properties and steam reforming efficiency was established. The lower reducibility of Co/CeO₂ catalysts, associated with the formation of Co³⁺ species, in Co₃O₄-like phase, can be accounted for the enhanced carbon tolerance of Co-based catalysts. Furthermore, the high concentration of surface oxygen species on Co/CeO₂ catalysts can be considered for their enhanced performance. On the other hand, the Cu-induced easier reducibility of bimetallic catalysts, in conjunction with carbon deposition and active phase sintering can be accounted for their inferior steam reforming performance. Irreversible changes in the redox properties of Cu-based catalysts, taking place under reaction conditions, could be resulted to ceria deactivation thus hindering the redox process to keep on.     

Biogas reforming for hydrogen production over mesoporous Ni2xCe1−xO2 catalysts

Biogas reforming for hydrogen production over mesoporous Ni_2xCe_1−xO₂ catalysts were proposed in this study. Mesoporous Ni_2xCe_1−xO₂ (x = 0.05, 0.13, 0.2) was prepared by a reverse precipitation method. The effects of nickel content were investigated in physicochemical properties and catalytic activities. All of the catalysts were reduced with 10% H₂/Ar at 600 °C before reactions, the reduced catalysts were found to be active for both dry and steam reforming of methane (CH₄:CO₂:H₂O = 3:1:2) to produce hydrogen and syngas. The studies were firstly carried out by temperature program reaction from 400 °C to 900 °C to verify the activity of temperature dependency. The long-term stability analysis was also studied at 700 °C for 24 h. Commercial catalyst (R67) was also employed for a comparative purpose.     

Carbon dioxide reforming of methane in a SrCe0.7Zr0.2Eu0.1O3−δ proton conducting membrane reactor

Utilizing CO₂ for fuel production holds the promise for reduced carbon energy cycles. In this paper we demonstrate a membrane reactor, integrating catalytic CO₂ reforming of methane with in-situ H₂ separation, that results in increased CO₂ and CH₄ conversion and H₂ production compared to a Ni catalyst alone. The tubular proton-conducting SrCe_0.7Zr_0.2Eu_0.1O_3−δ membrane reactor demonstrates that the addition of the membrane improves CO₂ conversion, due to in-situ H₂ removal, by 10% and 30% at 900 °C for CH₄/CO₂ = 1/1 and CH₄/CO₂/H₂O = 2/1/1 feed ratios, respectively. It also improves total H₂ production at 900 °C by 15% and 18% for CH₄/CO₂ = 1/1 and CH₄/CO₂/H₂O = 2/1/1, respectively. Further, the H₂/CO in the reactor side effluent can be adjusted for subsequent desired Fischer-Tropsch products by combining CO₂ reforming and steam reforming of methane.     

Enhanced ethanol steam reforming by CO2 absorption using CaO,CaO*MgO or Na2ZrO3

This paper presents results of thermodynamic analysis and experimental evaluation of hydrogen production by steam reforming of ethanol (SRE) combined with CO₂ absorption using a mixture of a solid absorbent (CaO, CaO*MgO and Na₂ZrO₃) and a Ni/Al₂O₃ catalyst. Thermodynamic analysis results indicate that a maximum of 69.5% H₂ (dry basis) is feasible at 1 atm, H₂O/C₂H₅OH = 6 (molar ratio) and T = 600 °C. whereas, the addition of a CO₂ absorbent at 1 atm, T = 600 °C and H₂O/C₂H₅OH/Absorbent = 6:1:2.5, produced a H₂ concentration of 96.6, 94.1, and 92.2% using CaO, CaO*MgO, and Na₂ZrO₃, respectively. SRE experimental evaluation achieved a maximum of 60% H₂. While combining SRE and a CO₂ absorbent exhibited a concentration of 96, 94, and 90% employing CaO, CaO*MgO, and Na₂ZrO₃, respectively at 1 atm, T = 600 °C, SV = 414 h⁻¹ and H₂O/C₂H₅OH/absorbent = 6:1:2.5 (molar ratio).     

Promotional effect of alkaline earth over Ni-La2O3 catalyst for CO2 reforming of CH4: Role of surface oxygen species on H2 production and carbon suppression

Alkaline earth elements (Mg, Ca and Sr) on Ni-La₂O₃ catalyst have been investigated as promoters for syngas production from dry CO₂ reforming of methane (DRM). The catalysis results of DRM performance at 600 °C show that the Sr-doped Ni-La₂O₃ catalyst not only yields the highest CH₄ and CO₂ conversions (∼78% and ∼60%) and highest H₂ production (∼42% by vol.) but also has the lowest carbon deposition over the catalyst surface. The XPS, O₂-TPD, H₂-TPR and FTIR results show that the excellent performance over the Sr-doped Ni-La₂O₃ catalyst is attributed to the presence of a high amount of lattice oxygen surface species which promotes C-H activation in DRM reaction, resulting in high H₂ production. Moreover, these surface oxygen species on the Ni-SDL catalyst can adsorb CO₂ molecules to form bidentate carbonate species, which can then react with the surface carbon species formed during DRM, resulting in higher CO₂ conversion and lower carbon formation.     

Effect of Ce on 5 wt% Ni/ZSM-5 catalysts in the CO2 reforming of CH4 reaction

The aim of this study is to investigate the promotional effect of Ce on Ni/ZSM-5 catalysts in the CO₂ reforming of CH₄ reaction. The evaluation of the catalytic performances of the composite catalysts was conducted in a fixed-bed reactor at atmospheric pressure. The influencing factors, including temperature, Ni and Ce loadings, molar feed ratio of CO₂/CH₄, and time-on-stream (TOS), were investigated. The characteristics of the catalysts were checked with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The reduction and the basic properties of the composite catalysts were elucidated by temperature-programmed reduction by H₂ (H₂-TPR) and temperature-programmed desorption of CO₂ (CO₂-TPD), respectively. The reactivity of deposited carbon was studied by sequential temperature-programmed surface reaction of CH₄ (CH₄-TPSR) and temperature-programmed oxidation using CO₂ and O₂ (CO₂-TPO and O₂-TPO). Results indicate that higher CH₄ conversion, H₂ selectivity, and desired H₂/CO ratio for 5 wt% Ni & 5 wt% Ce/ZSM-5 could be achieved with CO₂/CH₄ feed ratio close to unity over the temperature range of 500–900 °C. Moreover, the addition of Ce could not only promote CH₄ decomposition for H₂ production but also the gasification of deposited carbon with CO₂. The dispersion of Ni particles could be improved with Ce presence as well. A partial reduction of CeO₂ to CeAlO₃ was observed from XPS spectra over 5 wt% Ni & 5 wt% Ce/ZSM-5 after H₂ reduction and 24 h CO₂–CH₄ reforming reaction. Benefiting from the introduction of 5 wt% Ce, the calculated apparent activation energies of CH₄ and CO₂ over the temperature range of 700–900 °C could be reduced by 30% and 40%, respectively.     

Synthesis gas production in the combined CO2 reforming with partial oxidation of methane over Ce-promoted Ni/SiO2 catalysts

A series of nickel-based catalyst supported on silica (Ni/SiO₂) with different loading of Ce/Ni (molar ratio ranging from 0.17 to 0.84) were prepared using conventional co-impregnation method and were applied to synthesis gas production in the combination of CO₂ reforming with partial oxidation of methane. Among the cerium-containing catalysts, the cerium-rich ones exhibited the higher activity and stability than the cerium-low ones. The temperature-programmed reduction (TPR) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS) analysis revealed that the addition of CeO₂ reduced the chemical interaction between Ni and support, resulting in an increase in reducibility and dispersion of Ni. Over NiCe-x/SiO₂ (x = 0.17, 0.50, 0.67, 0.84) catalysts, the reduction peak in TPR profiles shifted to the higher temperature with increasing Ce/Ni molar ratio, which was attributed to the smaller metallic nickel size of the reduced catalysts. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) for the post-reaction catalysts confirmed that the promoter retained the metallic nickel species and prevented the metal particle growth at high reaction temperature. The NiCe-0.84/SiO₂ catalyst with small Ni particle size exhibited the stable activity with the constant H₂/CO molar ratio of 1.2 during 6-h reaction in the combination of CO₂ reforming with partial oxidation of methane at 850 °C and atmospheric pressure.     

Syngas production by CO2 reforming of coke oven gas over Ni/La2O3–ZrO2 catalysts

Syngas production by CO₂ reforming of coke oven gas (COG) was studied in a fixed-bed reactor over Ni/La₂O₃–ZrO₂ catalysts. The catalysts were prepared by sol–gel technique and tested by XRF, BET, XRD, H₂-TPR, TEM and TG–DSC. The influence of nickel loadings and calcination temperature of the catalysts on reforming reaction was measured. The characterization results revealed that all of the catalysts present excellent resistance to coking. The catalyst with appropriate nickel content and calcination temperature has better dispersion of active metal and higher conversion. It is found that the Ni/La₂O₃–ZrO₂ catalyst with 10 wt% nickel loading provides the best catalytic activity with the conversions of CH₄ and CO₂ both more than 95% at 800 °C under the atmospheric pressure. The Ni/La₂O₃–ZrO₂ catalysts show excellent catalytic performance and anti-carbon property, which will be of great prospects for catalytic CO₂ reforming of COG in the future.     

Kinetics of the water-gas shift reaction over a La0.7Ce0.2FeO3 perovskite-like catalyst using simulated coal-derived syngas at high temperature

The kinetics of the water-gas shift (WGS) reaction over a novel La_0.7Ce_0.2FeO₃ perovskite-like catalyst is investigated using simulated coal-derived syngas at temperatures of 550 °C and 600 °C which are higher than the maximum operating temperature limit for conventional high temperature WGS catalysts. The influences of CO, CO₂, H₂O and H₂ concentration on WGS reaction rate are determined using selected gas compositions that might be encountered in a coal-based gasification system. An empirical power-law rate model used in this study is found to correlate well with experimental data with good accuracy. Kinetics parameters over La_0.7Ce_0.2FeO₃ obtained in this study are mostly in agreement with those previously measured using Fe-Cr based commercial catalysts in a range of relatively lower temperatures (300-500 °C).     

High hydrogen yield and purity from palm empty fruit bunch and pine pyrolysis oils

The benefits of CO₂ sorption enhanced steam reforming using calcined dolomite were demonstrated for the production of hydrogen from highly oxygenated pyrolysis oils of the agricultural waste palm empty fruit bunches (PEFB) and pine wood. At 1 atm in a down-flow packed bed reactor at 600 °C, the best molar steam to carbon ratios were between 2 and 3 using a Ni catalyst. After incorporating steam-activated calcined dolomite as the CO₂ sorbent in the reactor bed, the H₂ yield from the moisture free PEFB oil increased from 9.5 to 10.4 wt.% while that of the pine oil increased from 9.9 to 13.9 wt.%. The hydrogen purity also rose from 68 to 96% and from 54 to 87% for the PEFB and pine oils respectively, demonstrating very substantial sorption enhancement effects.     

LaNiO3@SiO2 core–shell nano-particles for the dry reforming of CH4 in the dielectric barrier discharge plasma

LaNiO₃@SiO₂ core–shell nano-particles were prepared by coating LaNiO₃ nano-particles with SiO₂ and then employed to catalyze the dry reforming of CH₄ to produce syngas (CO + H₂) in a coaxial dielectric barrier discharge (DBD) plasma reactor under ambient conditions. Compared to the traditional Ni-based catalysts (Ni/SiO₂, LaNiO₃/SiO₂ and LaNiO₃), LaNiO₃@SiO₂ exhibited better catalytic performance in the dry reforming of CH₄ in DBD plasma reactor, such as higher reactant conversion and product selectivity, and excellent catalytic stability. The conversions of CH₄ and CO₂ reached 88.31% and 77.76%, and selectivities of CO and H₂ were 92.43% and 83.65%, respectively. Results manifested the core–shell structure endowed LaNiO₃@SiO₂ with excellent catalytic performance because the SiO₂ shell was capable of preventing Ni from sintering and mitigating carbon deposition during the reaction.     

Integrated catalytic adsorption (ICA) steam gasification system for enhanced hydrogen production using palm kernel shell

This paper investigates the integrated catalytic adsorption (ICA) steam gasification of palm kernel shell for hydrogen rich gas production using pilot scale fluidized bed gasifier under atmospheric condition. The effect of temperature (600–750 °C) and steam to biomass ratio (1.5–2.5 wt/wt) on hydrogen (H₂) yield, product gas composition, gas yield, char yield, gasification and carbon conversion efficiency, and lower heating values are studied. The results show that H₂ hydrogen composition of 82.11 vol% is achieved at temperature of 675 °C, and negligible carbon dioxide (CO₂) composition is observed at 600 °C and 675 °C at a constant steam to biomass ratio of 2.0 wt/wt. In addition, maximum H₂ yield of 150 g/kg biomass is observed at 750 °C and at steam to biomass ratio of 2.0 wt/wt. A good heating value of product gas which is 14.37 MJ/Nm³ is obtained at 600 °C and steam to biomass ratio of 2.0 wt/wt. Temperature and steam to biomass ratio both enhanced H₂ yield but temperature is the most influential factor. Utilization of adsorbent and catalyst produced higher H₂ composition, yield and gas heating values as demonstrated by biomass catalytic steam gasification and steam gasification with in situ CO₂ adsorbent.     

A novel catalyst–sorbent system for an efficient H2 production with in-situ CO2 capture

This paper presents an experimental investigation for an improved process of sorption-enhanced steam reforming of methane in an admixture fixed bed reactor. A highly active Rh/Ce_αZr_1−αO₂ catalyst and K₂CO₃-promoted hydrotalcite are utilized as novel catalyst/sorbent materials for an efficient H₂ production with in situ CO₂ capture at low temperature (450–500 °C). The process performance is demonstrated in response to temperature (400–500 °C), pressure (1.5–6.0 bar), and steam/carbon ratio (3–6). Thus, direct production of high H₂ purity and fuel conversion >99% is achieved with low level of carbon oxides impurities (<100 ppm). A maximum enhancement of 162% in CH₄ conversion is obtained at a temperature of 450 °C and a pressure of 6 bar using a steam/carbon molar ratio of 4. The high catalyst activity of Rh yields an enhanced CH₄ conversion using much lower catalyst/sorbent bed composition and much smaller reactor size than Ni-based sorption enhanced processes at low temperature. The cyclic stability of the process is demonstrated over a series of 30 sorption/desorption cycles. The sorbent exhibited a stable performance in terms of the CO₂ working sorption capacity and the corresponding CH₄ conversion obtained in the sorption enhanced process. The process showed a good thermal stability in the temperature range of 400–500 °C. The effects of the sorbent regeneration time and the purge stream humidity on the achieved CH₄ conversion are also studied. Using steam purge is beneficial for high degree of CO₂ recovery from the sorbent.     

Carbon dioxide reforming of methane to synthesis gas over Ni/Si3N4 catalysts

Silicon nitride supported nickel catalyst prepared by impregnation using nickel nitrate solution was employed for the carbon dioxide reforming of methane. The catalyst was tested at 800 °C under atmospheric pressure. The influences of Ni loading and calcination temperature on the catalytic performance were investigated. It was found that the nickel loading and calcination temperature strongly influenced the catalytic performance. Over the 7 wt. % Ni/Si₃N₄ catalyst calcined at 400 °C, the conversions of CH₄ and CO₂ can achieve 95% and 91%, respectively. Appropriate interaction between the metal and the basic support makes the catalyst more resistant to sintering and coking, and thus an excellent stability.