Co and La supported on Zn-Hydrotalcite-derived material as efficient catalyst for ethanol steam reforming

Four samples of Zn-hydrotalcite containing different amounts of Co (5, 10, 20, and 30 wt%) have been synthesized and tested in the steam reforming of ethanol. The best results were obtained with the sample containing 20 wt% of Co (20CoHT), with a complete conversion of ethanol and yields to hydrogen close to the equilibrium (73 mol.%). The physicochemical characterization of the samples by DRX, BET area and TPR indicates that the excellent performance exhibited by the sample containing 20 wt% of Co is due to the higher percentage of reduced cobalt and lower crystallite size of metallic cobalt present in this sample (11 nm). Additional studies have been carried out to improve the stability of this catalytic material against deactivation by the incorporation of 1 wt% of La. Stability studies were carried out using an industrial alcoholic waste as feed. Deactivation after 24 h of reaction time was found lower for the catalyst containing La (20CoLaHT), confirming the positive effect of lanthanum on the catalytic stability. The results presented here show that it is possible to prepare a catalyst based on Co supported on Zn-hydrotalcite and promoted with La with improved ethanol conversion, high hydrogen selectivity, and high stability to produce hydrogen by the steam reforming of an industrial alcoholic waste without commercial value.     

Effects of attapulgite-supported transition metals catalysts on glycerol steam reforming for hydrogen production

The attapulgite supported transition metals (Ni, Cu, Co or Fe) catalysts were prepared by precipitation method at constant loading (10 wt%) and investigated in the glycerol steam reforming reaction for H₂ production under 400–750 °C, water/glycerol (W/G) = 3, N₂ flow ratio = 0.16 L/min and WHSV = 6.46 h^?1. The as-prepared catalysts were characterized by N₂ adsorption-desorption, XRD, H₂-TPR and TEM-EDS. The results shown different active metals presented various crystalline sizes and reduction properties. The experimental results revealed Ni/ATP and Co/ATP catalysts had more active for glycerol steam reforming than Cu/ATP and Fe/ATP catalysts, due to the fact that active metal Ni and Co have superior capacity to promote the necessary CC rupture and facilitate the water gas shift reaction. In addition, the results revealed that CH₄ production was favored at low temperatures while CO production was presented at high temperatures, which were induced by the different reaction networks over catalysts. In addition, the stability test shown all catalysts had different various degrees of inactivation, resulting from the sintering of active metals and carbon deposition. The characterizations of XRD, TEM and TG-DTG for spent catalysts revealed the smallest amount of carbon deposited for Cu/ATP, which was attributed to the lowest Cu particle size. Additionally, two different types of carbon was found, namely filamentous carbon for Ni and Co/ATP and encapsulating carbon for Cu and Fe/ATP.     

Cu promoted Ni-Co/hydrotalcite catalyst for improved hydrogen production in comparison with several modified Ni-based catalysts via steam reforming of ethanol

Enhanced hydrogen production via catalytic steam reforming of ethanol has a huge potential. In the present investigation, several combinations of mixed metal oxide supported catalysts were evaluated for efficient and economical hydrogen generation from ethanol. The comparison was carried out in terms of ethanol conversion, hydrogen yield and cyclic stability over various catalyst-support systems. Several nickel based supported catalysts namely, Ni/MgO, Ni/Al₂O₃, Ni/CeO₂ and Ni/ZrO₂ were studied in this work among which Ni/MgO and Ni/Al₂O₃ showed satisfactory activity and stability for hydrogen production. Thereafter Ni/hydrotalcite (HTc)-type material was employed to combine features of the above catalysts which showed more than 90% ethanol conversion and yielded 82 mol% of hydrogen at optimized conditions. Finally, a novel combination of Cu promoted Ni-Co/HTc was synthesized and tested for improved hydrogen production. It showed almost complete conversion of ethanol (98.3%) with hydrogen yield of 83% at much lower temperature (673 K). The process conditions were optimized by studying effects of temperature, S/C ratio and GHSV on hydrogen production. Cu-Ni-Co/HTc also remained stable for up to 4 cycles justifying its multi-cycle activity, selectivity and durability. Such novel combination of catalyst-support system assists in improved hydrogen production in a sustainable manner.     

Hydrogen production by glycerol steam reforming with in situ hydrogen separation: A thermodynamic investigation

Thermodynamic features of hydrogen production by glycerol steam reforming with in situ hydrogen extraction have been studied with the method of Gibbs free energy minimization. The effects of pressure (1–5 atm), temperature (600–1000 K), water to glycerol ratio (WGR, 3–12) and fraction of H₂ removal (f, 0–1) on the reforming reactions and carbon formation were investigated. The results suggest separation of hydrogen in situ can substantially enhance hydrogen production from glycerol steam reforming, as 7 mol (stoichiometric value) of hydrogen can be obtained even at 600 K due to the hydrogen extraction. It is demonstrated that atmospheric pressure and a WGR of 9 are suitable for hydrogen production and the optimum temperature for glycerol steam reforming with in situ hydrogen removal is between 825 and 875 K, 100 K lower than that achieved typically without hydrogen separation. Furthermore, the detrimental influence of increasing pressure in terms of hydrogen production becomes marginal above 800 K with a high fraction of H₂ removal (i.e., f = 0.99). High temperature and WGR are favorable to inhibit carbon production.     

Exergy analysis of glycerol steam reforming in a heat recovery reactor

A detailed exergy analysis was performed for the steam reforming process of glycerol by means of a series of experiments in a bench scale apparatus. The reforming was conducted in a fixed bed reactor, which operated in heat recovery mode by extracting the demanded energy from hot exhaust gases provided by a diesel engine. In order to determine the role of the main operational parameters into the exergy efficiency of the studied process, the experiments were carried out with glycerol feed concentrations in water ranging from 10% up to 90% weight, whereas the outlet reactor temperature was varied from 600 °C up to 800 °C. Detailed exergy balances revealed a compromise between the exergy destruction within the reforming reactor and liquid separator versus the exergy losses associated to the tar and char outputs. This trade-off was favourable to the 50% and 70% glycerol feed concentration regimes and plateaus of about 74% exergy efficiency and 24 MJ/kg dry syngas exergy content were verified from 650 to 800 °C reactor temperatures.     

Performance evaluation of PdAg membrane reactor in glycerol steam reforming process: Development of the CFD model

In the present paper, a CFD modeling of palladium membrane reactor, in which hydrogen produced through glycerol steam reforming, is presented. A comprehensive and precise kinetic and permeation model was used. On the basis of the equations and assumptions, an excellent agreement between model prediction and experimental data was achieved. Pressure, velocity and concentration distribution of various component within the Membrane Reactor (MR) were predicted. Moreover, the performance of both a Traditional Reactor (TR) and a MR was compared in various condition. The effects of some operating conditions such as temperature, pressure, feed flow rate and flow pattern on the glycerol conversion, hydrogen recovery and CO selectivity were evaluated. The most effective parameter was pressure: increasing it from 1 to 10 bar in co-current MR, the glycerol conversion, H2 recovery and CO selectivity were shifted from 46%, 17% and 6.6%–81%, 56% and 0.8%, respectively. The CFD model indicates that the performance of glycerol steam reforming improves when MR is used instead of TR. At various operating conditions the glycerol convertion enhanced 10–64% and CO selectivity reduced 7.5–99.0% in the MR when compared with the TR.     

Methane steam reforming: Kinetics and modeling over coating catalyst in micro-channel reactor

Kinetics of methane steam reforming for hydrogen production has been studied through experiment in a micro-channel reactor over coating catalyst. The catalyst coating prepared by cold spray on stainless steel substrate is based on a mixture of Ni–Al oxides which is normally employed in industry for methane primary steam reforming. Two kinetic laws namely parallel as well as inverse models have been derived at atmospheric pressure, and power law type kinetics have been established using non-linear least squares optimization. With the above kinetics, simulation study has been carried out to find out temperature distribution in the micro-channel over coating catalyst at two different types of boundary conditions. The results show a quite different “cold spot” character and reactants, products distribution character in the reaction channel due to its own distinct heat and mass transfer features. The kinetics and simulation study results can be applied in aid of micro-channel reactor design, and suggestion has been proposed for catalytic coating preparation and optimization.     

Ni supported on CaO-MgO-Al2O3 as a highly selective and stable catalyst for H2 production via the glycerol steam reforming reaction

A comparative study of the GSR performance for Ni/CaO-MgO-Al₂O₃ and Ni/Al₂O₃ catalysts is reported. Catalysts were synthesized applying the wet impregnation method at a constant metal loading (8 wt %). Synthesized samples were characterized by N₂ adsorption/desorption, ICP, BET, XRD, NH₃-TPD, CO₂-TPD, H₂-TPR, XPS, TEM, STEM-HAADF and EDS. The carbon deposited on their surface under reaction conditions was characterized by TPO, Raman and TEM. It was proven that the use of CaO-MgO as alumina modifiers leads to smaller nickel species crystallite size, increased basicity and surface amount of Ni⁰ phase. Thus, it increases the conversion to gaseous products favoring H₂ and CO₂ production to the detriment of CO formation, by enhancing the water gas-shift (WGS) reaction. No liquid products were produced by the Ni/modAl catalyst over 550 °C, whereas time on stream results confirmed that deactivation can be prevented, as apart from decreasing the amount of coke deposition the nature of carbon was altered towards less graphitic and more defective structures.     

Catalytic performance of a high-cell-density Ni honeycomb catalyst for methane steam reforming

The catalysis of methane steam reforming (MSR) by pure Ni honeycombs with high cell density of 2300 cells per square inch (cpsi) was investigated to develop efficient and inexpensive catalysts for hydrogen production. The Ni honeycomb catalyst was assembled using 30-μm-thick Ni foils, and showed much higher activity than that of a Ni honeycomb catalyst with cell density of 700 cpsi at a steam-to-carbon ratio of 1.36 and a gas hourly space velocity of 6400 h^?1 in a temperature range of 873–1173 K. Notably, the activity increased approximately proportional to the increasing geometric specific surface area of the honeycombs. The turnover rate of the Ni honeycomb catalyst was higher than that of supported Ni catalysts. The changes in chemical state of the Ni catalyst during hydrogen reduction and MSR reaction were analyzed by in situ X-ray absorption fine structure spectroscopy, which revealed that deactivation was mainly due to oxidation of the surface Ni atoms. These results demonstrated that the high-cell-density Ni honeycomb catalyst exhibits good performance for MSR reaction, and easy regeneration of the deactivated Ni honeycomb catalyst is possible only via hydrogen reduction.     

Cu,Mg and Co effect on nickel-ceria supported catalysts for ethanol steam reforming reaction

Ethanol steam reforming is a promising reaction which produces hydrogen from bio and synthetic ethanol. In this study, the nano-structured Ni-based bimetallic supported catalysts containing Cu, Co and Mg were synthesized through impregnation method and characterized by XRD, BET, SEM, TPR and TPD analysis. The prepared catalysts were tested in steam reforming of ethanol in the S/C = 6, GHSV of 20,000 mL/(g_cat h) at the temperature range of 450–600 °C. Among the xNi/CeO₂ (x = 10, 13, 15 wt%) catalyst, the sample containing 13 wt% Ni with surface area of 64 m²/g showed the best performance with 89% ethanol conversion and 71% H₂ selectivity as well as low CO selectivity of 8% at 600 °C and The addition of Cu, Mg, and Co to catalyst structure were evaluated and it was found that the nature of second metal has a strong influence on the catalyst selectivity for H₂ production. Considering to results of TPR analysis, the 13Ni–4Cu/CeO₂ catalyst showed proper reduction which caused in better activity. On the other side based on TPD analysis, the more basic property of 13Ni–4Mg/CeO₂ bimetallic catalyst provided a better condition to methane steam reforming, leading to lower CH₄ selectivity and consequently more H₂ production. The 13Ni–4Cu/CeO₂ exhibited the highest activity and lowest selectivity towards ethanol conversion and CO production about 99% and 4%, while the 13Ni–4Mg/CeO₂ catalyst possessed the highest H₂ selectivity and lowest CH₄ selectivity about 74% and 1% respectively at 600 °C. The Ni–Cu and Ni–Mg bimetallic catalysts shows good stability with time on stream.     

Mechanistic insights into methanol steam reforming over a ZnZr oxide catalyst with improved activity

Methanol steam reforming (MSR) holds great potential for mobile hydrogen production, but it still requires an active and stable catalyst. In this work, we report a high-performance ZnZr-0.5 composite oxide catalyst for this reaction, with a hydrogen production rate of 2.80 mol·g_cat^?1·h^?1 and CO₂ selectivity of 99.6% at a methanol space velocity of 22,762 mL·g_cat^?1·h^?1. It also exhibits superior long-term durability in the TOS test for more than 100 h. Such good activity results from a synergistic effect of ZnO–ZrO₂ dual sites. ZrO₂ is capable of stabilizing and storing more CH₃O1 and HCOO1 intermediates while ZnO is in charge of the dehydrogenation of these key intermediates. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and chemisorption results reveal that the MSR reaction experiences successively the hydrolysis of methyl formate and dehydrogenation of formate. More importantly, it is found that H₂O significantly promotes the dehydrogenation of HCOO1 intermediate by directly participating in this reaction from pulse chemisorption experiments.     

Autothermal steam reforming of glycerol for hydrogen production over packed-bed and Pd/Ag alloy membrane reactors

In this study, glycerol, with its high H/C ratio feature, was steam reformed with oxygen to produce hydrogen in packed-bed and Pd/Ag membrane reactors. The addition of oxygen, which causes the partial oxidation, was to achieve thermal neutral for the energy saving purposes.     

Magnesium promoted hydrocalumite derived nickel catalysts for ethanol steam reforming

Hydrocalumite derived nickel (Ni) catalysts with different loading of magnesium (Mg) (7.5/10/15 wt%, as promoters) were for the first time prepared and tested for ethanol steam reforming (ESR) in this work. The catalytic performances of different Mg promoted catalysts were mainly evaluated in the temperature range between 550 and 700 °C as determined by thermodynamic simulation. Experimental results showed that the optimal reaction temperature was 650 °C in terms of the hydrogen yields for these ESR catalysts, especially for 15Ni7.5Mg/HCa which presented a remarkable catalytic performance. Its hydrogen yields reached 90% while ethanol was almost fully converted at 650 °C. Based on the characterization results, it's believed that 15Ni7.5Mg/HCa with a certain amount of Mg loading can get the smallest Ni⁰ crystallite sizes, better H₂ reducibility and suitable basicities on strong basic sites. The catalytic performances of ESR catalysts were mainly related to the Ni⁰ crystallite size, reducibility and basicity for the prepared hydrocalumites derived Ni catalysts, and 15Ni7.5Mg/HCa could be considered as one of the best catalysts for ESR.     

Hydrogen from glycerol steam reforming with a platinum catalyst supported on a SiO2-C composite

This work studies 2 wt% Pt catalysts. The support is a SiO₂-C composite whose main features are a high specific surface due to its mesoporosity, a higher thermal stability than the C support, and the absence of surface acid sites which could promote the dehydration reactions that produce coke precursors. The Pt/SiO₂-C catalyst has very small metallic particles (d_va = 1.37 nm) that favor the CC bond cleavage reactions which allow obtaining total gas conversion at 450 °C. With this catalyst, it is possible to obtain high yields to H₂, between 4 and 5, which indicates that the active sites promote the WGS reaction, even with glycerol concentrations of 30 and 50%. Pt/SiO₂-C is a very stable catalyst since it loses only 10% of its initial activity after 66 h on stream and is resistant to sintering and coke deposition.     

Natural gas steam reforming for hydrogen production over metal monolith catalyst with efficient heat-transfer

Heat transfer performance of the natural gas (NG) steam reforming in a reactor bed with metal monolith catalyst has been evaluated in comparison with that in the conventional packed bed with pellet catalysts. 2%Ru/Al₂O₃ catalyst with high intrinsic activity has been wash-coated on metal monolith substrates or used as it was for the packed bed application. The prepared metal monolith catalyst has been applied for NG steam reforming to increase heat-transfer efficiency. Under the same degree of temperature gradient from the furnace wall to the catalyst bed, the heat flux obtained in the monolithic bed reactor was about twice higher than that in the packed bed reactor. Maximum heat transfer coefficient achieved in this study for the former was 0.65 kW/m² K, while that for the latter was 0.3 kW/m² K. This is mainly due to enhanced heat-transfer via metal monolith catalyst.     

Hydrogen generation via ethanol steam reforming over Co/HAp catalysts

The catalytic activity of calcium hydroxyapatite (HAp) supported cobalt nanoparticles in ethanol steam reforming (SRE) was investigated. Co was supported on hydrothermally prepared HAp by incipient wetness impregnation method. Co/HAp catalysts were characterized through XRD, FT-IR and Raman spectroscopy, TEM, SEM/EDS, N₂ physisorption, TG and TPR-H₂. Results showed that spinel cobalt oxide is reduced to CoO and Co and these species are responsible for catalytic activity for hydrogen production via SRE process. The main reactions over Co/HAp are incomplete steam reforming and dehydrogenation of ethanol. Reforming experiment over pre-reduced sample indicated a negative impact of H₂ treatment on hydrogen production. The best catalytic properties (${\text{Y}}_{{\text{H}}_2}$ and C_EtOH) were obtained over 5%Co/HAp catalyst.     

Conversion of biodiesel synthesis waste to hydrogen in membrane reactor: Theoretical study of glycerol steam reforming

Hydrogen production from waste glycerol, mainly producible as a by-product of biodiesel synthesis, is investigated as an attractive opportunity for exploiting renewable energy sources for further applications. Glycerol steam reforming using membrane technology was modeled by taking into accounts the maim transport phenomena, thermodynamic criteria and chemical process kinetics. A sensitivity analysis of operating conditions was made for key performance metrics such as glycerol conversion, hydrogen yield and hydrogen recovery. Glycerol conversion intensifies with enhancement of operating pressure and temperature, whereas high feed molar ratio and sweep ratio have limiting effect. Hydrogen permeation and subsequently, hydrogen recovery facilitates with increasing sweep gas ratio and sweep gas temperature. Hydrogen recovery enhances from 70% to 99% with increasing temperature from 350 to 500 °C at feed molar ratio of 3. Also, hydrogen recovery improves from 50% to 71% with increasing sweep ratio from 0 to 20 at 350 °C and 1 bar.     

Hydrogen production from glycerol steam reforming over Ni/La/Co/Al2O3 catalyst

Hydrogen production by steam reforming reaction of glycerol over Co/La/Ni-Al₂O₃ was studied in tubular fixed-bed reactor. The influences of operating parameters such as temperature, steam/carbon ratio, and weight hourly space velocity (WHSV) on hydrogen yield and carbon conversion were examined under atmospheric pressure. The results showed that carbon conversion increased with the increase of temperature and steam-to-carbon mole ratio (S/C). At 700°C, S/C=3:1, and WHSV=2.5h^?1, hydrogen yield and potential hydrogen yield were up to 77.64% and 89.64%, respectively; meanwhile, the carbon conversion reached 96.36%.     

Comparative analysis on sorption enhanced steam reforming and conventional steam reforming of hydroxyacetone for hydrogen production: Thermodynamic modeling

The chemical thermodynamics of sorption enhanced steam reforming (SESR) of hydroxyacetone for hydrogen production were investigated and contrasted with hydroxyacetone steam reforming (SR) by means of Gibbs free energy minimization principle and response reactions (RERs) method. Hydrogen is mainly derived methane steam reforming reaction from and water gas shift reaction. The former reaction contributes more than the latter one to hydrogen production below 550 °C and at higher temperature the latter one tends to dominate. The maximum hydrogen concentration is 70% in SR, which is far below hydrogen purities required by fuel cells. In SESR, hydrogen purities are over 99% in 525–550 °C with a WHMR greater than 8 and a CHMR of 6. The optimum temperature for SESR is approximately 125 °C lower than that for SR. In comparison with SR, SESR has the advantage of almost complete inhibition of coke formation in 200–1200 °C for WHMR ≥ 3.