Effect of Ni Loading and Ce_(x)Zr_(1-x)O_(2) Promoter on Ni-Based SBA-15 Catalysts for Steam Reforming of Methane

A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at at- mospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800 ℃ for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.

Hydrogen and syngas production from two-step steam reforming of methane using CeO_2 as oxygen carrier

CeO2 oxygen carrier was prepared by precipitation method and tested by two-step steam reforming of methane （SRM）. Two-step SRM for hydrogen and syngas generation is investigated in a fixed-bed reactor. Methane is directly converted to syngas at a H2/CO ratio close to 2 ： 1 at a high temperature （above 750 °C） by the lattice oxygen of CeO2; methane cracking is found when the reduction degree of CeO2 was above 5.0% at 850 °C in methane isothermal reaction. CeO2？δ obtained from methane isothermal reaction can split water to generate CO-free hydrogen and renew its lattice oxygen at 700 °C; simultaneously, deposited carbon is selectively oxidized to CO2 by steam following the reaction （C＋2H2O→CO2＋2H2）. Slight deactivation in terms of amounts of desired products （syngas and hydrogen） is observed in ten repetitive two-step SRM process due to the carbon deposition on CeO2 surface as well as sintering of CeO2.

Improved catalytic performance of Ni catalysts for steam methane reforming in a micro-channel reactor

Milliseconds process to produce hydrogen by steam methane reforming （SMR） reaction, based on Ni catalyst rather than noble catalyst such as Pd, Rh or Ru, in micro-channel reactors has been paid more and more attentions in recent years. This work aimed to further improve the catalytic performance of nickel-based catalyst by the introduction of additives, i.e., MgO and FeO, prepared by impregnation method on the micro-channels made of metal-ceramic complex substrate. The prepared catalysts were tested in the same micro-channel reactor by switching the catalyst plates. The results showed that among the tested catalysts Ni-Mg catalyst had the highest activity, especially under harsh conditions, i.e., at high space velocity and/or low reaction temperature. Moreover, the catalyst activity and selectivity were stable during the 12 h on stream test even when the ratio of steam to carbon （SIC） was as low as 1.0. The addition of MgO promoted the active Ni species to have a good dispersion on the substrate, leading to a better catalytic performance for SMR reaction.

Effect of MgO promoter on Ni-based SBA-15 catalysts for combined steam and carbon dioxide reforming of methane

A series of Ni/SBA-15 catalysts with Ni contents ranging from 5 wt% to 15 wt%, as well as another series of 10%Ni/MgO/SBA-15 catalysts, in which the range of the MgO content was from 1 wt% to 7 wt%, were prepared, and their catalytic performances for the reaction of combined steam and carbon dioxide reforming of methane were investigated in a continuous flow microreactor. The structures of the catalysts were characterized using the XRD, H2-TPR and CO2-TPD techniques. The results indicated that the CO selectivity for this reaction was very close to 100%, and the H2/CO ratio of the product gas could be controlled by changing the H2O/CO2 molar ratio of the feed gas. The simultaneous and plentiful existing of steam and CO2 had a significant influence on the catalytic performance of the 10%Ni/SBA-15 catalyst without modification. After reacting at 850 °C for 120 h over this catalyst, the CH4 conversion dropped from 98% to 85%, and the CO2 conversion decreased from 86% to 53%. However, the 10%Ni/3%MgO/SBA-15 catalyst exhibited a much better catalytic performance, and after reacting for 620 h, the CO2 conversion over this catalyst dropped from 92% to around 77%, while the CH4 conversion was not decreased. Oxidation of the Ni0 species as well as carbon deposition during the reaction were the main reasons for the deactivation of the catalyst without modification. On the other hand, modification by the MgO promoter improved the dispersion of the Ni0 species, and enhanced the CO2 adsorption affinity which in turn depressed the occurring of carbon deposition, and thus retarded the deactivation process.

Catalytic steam methane reforming enhanced by CO_2 capture on CaO based bi-functional compounds

Sorption enhanced steam methane reforming（SE-SMR） was performed to maximize hydrogen production and contemporary remove COfrom the product stream using bi-functional sorbent-catalyst compounds.Samples were tested at two different scales: micro and laboratory. The CaO amount varied in the CaO-CaAlOsorbent system synthesized by wet mixing(CaO content of 100 wt%, 56 wt%, 30 wt%, or 0 wt% and balance of CaAlO) which were upgraded to bi-functional compounds by impregnation of 3 wt% of Ni. Nitrogen adsorption（BET/BJH）, X-Ray Diffraction（XRD）, Temperature-Programmed Reduction（TPR） and Scanning and Transmission Electronic Microscopy（SEM and TEM, respectively） analyses were performed to characterize structural and textural properties and reducibility of the bi-functional materials and evaluate their catalytic behavior. A fixed sorbent composition CaO-CaAlO(56 wt% of CaO and CaAlObalance), was chosen to study the effect of different weight hourly space times（WHST） and CHstream compositions in SE-SMR activity. Impregnated mayenite at both micro and laboratory scales showed stable Hcontent of almost 74%, with CHconversion of 72% similarly to the values reported by the sample containing 30 wt% of CaO in the post-breakthrough.Sample with 30 wt% of CaO showed promisingly behavior, enhancing Hcontent up to almost 94.5%.When the sorption enhanced reaction is performed roughly 89% of CHconversion is achieved, and after the pre-breakthrough, the catalyst worked at the thermodynamic level. During cycling sorption/regeneration experiments, even if COremoval efficiency slightly decreases, CHconversion and Hyield remain stable.

Tuning combined steam and dry reforming of methane for “metgas”production: A thermodynamic approach and state-of-the-art catalysts

Nowadays,combined steam and dry reforming of methane(CSDRM)is viewed as a new alternative for the production of high-quality syngas(termed as"metgas",H2:CO of 2.0)suitable for subsequent synthesis of methanol,considered as a promising renewable energy vector to substitute fossil fuel resources.Adequate operation conditions(molar feed composition,temperature and pressure)are required for the sole production of"metgas"while achieving high CH4,CO2 and H2O conversion levels.In this work,thermodynamic equilibrium analysis of CSDRM has been performed using Gibbs free energy minimization where;(i)the effect of temperature(range:200-1000℃),(ii)feed composition(stoichiometric ratio as compared to a feed under excess steam or excess carbon dioxide),(iii)pressure(range:1-20 bar)and,(iv)the presence of a gaseous diluent on coke yields,reactivity levels and selectivity towards"metgas"were investigated.Running CSDRM at a temperature of at least 800℃,a pressure of 1 bar and under a feed composition where CO2-H2O/CH4 is around 1.0,are optimum conditions for the theoretical production of"metgas"while minimizing C(S)formation for longer experimental catalytic runs.A second part of this work presents a review of the recent progresses in the design of(principally)Ni-based catalysts along with some mechanistic and kinetic modeling aspects for the targeted CSDRM reaction.As compared to noble metals,their high availability,low cost and good intrinsic activity levels are main reasons for increasing research dedications in understanding deactivation potentials and providing amelioration strategies for further development.Deactivation causes and main orientations towards designing deactivationresistant supported Ni nanoparticles are clearly addressed and analyzed.Reported procedures based on salient catalytic features(i.e.,acidity/basicity character,redox properties,oxygen mobility,metal-support interaction)and recently employed innovative tactics(such as confinement within mesoporous systems,stabilization through core shell structures or on carbide surfaces)are highlighted and their impact on Ni0reactivity and stability are discussed.The final aspect of this review encloses the major directions and trends for improving synthesis/preparation designs of Ni-based catalysts for the sake of upgrading their usage into industrially oriented combined reforming operations.

Steam reforming of methane over Ni catalysts prepared from hydrotalcite-type precursors: Catalytic activity and reaction kinetics

Ni/Mg–Al catalysts derived from hydrotalcite-type precursors were prepared by a co-precipitation technique and applied to steam reforming of methane. By comparison with Ni/γ-Al2O3 and Ni/α-Al2O3 catalysts prepared by incipient wetness impregnation, the Ni/Mg–Al catalyst presented much higher activity as a result of higher specific surface area and better Ni dispersion. The Ni/Mg–Al catalyst with a Ni/Mg/Al molar ratio of 0.5:2.5:1 exhibited the highest activity for steam methane reforming and was selected for kinetic investigation. With external and internal diffusion limitations eliminated, kinetic experiments were carried out at atmospheric pressure and over a temperature range of 823–973 K. The results demonstrated that the overall conversion of CH4 and the conversion of CH4 to CO2were strongly influenced by reaction temperature, residence time of reactants as well as molar ratio of steam to methane. A classical Langmuir–Hinshelwood kinetic model proposed by Xu and Froment(1989)fitted the experimental data with excellent agreement. The estimated adsorption parameters were consistent thermodynamically.

A Simulation Study of the Steam Reforming of Methaneina Fixed-Bed Reactor

In this work a one-dimensional mathematical model was developed to simulate methane conversion and hydrogen yield in a fixed-bed reactor filled with catalyst particles. For the reason that reforming reactions are sorely endothermic process, the heat is supplied to the reactor through electrical heating. The reforming reactions have been investigated from a modelling view point considering the effect of different temperatures ranging from 500℃ and 977℃ on the conversion of methane and hydrogen yield. Simulation results show that the steam reforming of methane in a fixed-bed reactor can efficiently store high temperature end thermal energy. When the operating temperature is increased to 977℃, the conversion of methane is 97.48% and the hydrogen yield is 2.2408. As a conclusion, the maximum thermochemical efficiency will be obtained under optimal operating temperature (977℃) and the steam/methane (3.86) ratio.

Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

The effects of temperature and pressure on the steam reforming of methane （CH4＋H2O→← 3H2＋CO） were investigated in a membrane reactor （MR） with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition （CVD） technique with a permeance for H2 of 6.0×10^-8 mol·m^-2.s^-1.Pa^-1 at 923 K. The results in a packed-bed reactor （PBR） were compared to those of the membrane reactor at various temperatures （773-923 K） and pressures （1-20 atm, 101.3-2026.5 kPa） using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73× 10^-6 mol·g^-1 .s^-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10^-6 mol·g^-1.s^-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature.

Methane Steam Reforming on Supported Nickel Based Catalysts. Effect of Oxide ZrO₂, La₂O₃and Nickel Composition

The catalytic properties of Ni (4 and 10 wt%) supported on both La2O3 and ZrO2 were investigated for the methane steam reforming reaction between 475℃ and 700℃ at atmospheric pressure. The catalysts were prepared by the impregnation method and characterized by several techniques (atomic absorption, BET method, X-ray diffraction and TG-TPO). The catalytic activity of Ni/support systems strongly depends on both of the nature and physico-chemical properties of the support. No deactivation was observed in catalytic systems, whatever the reaction temperature indicating high stability of the catalyst.

Methane Steam Reforming on Supported Nickel, Effect of Nickel Content for Product Hydrogen

The steam reforming of methane over NiO/ZnO mixed oxides with different nickel contents was studied. Solids to x% Ni/ZnO (x = 4 and 10%) were deposited on ZnO by impregnation from nickel nitrate solution;after vaporization the solid is calcined at 500°C for 6 h. The catalysts were characterized by X-ray diffraction (XRD) and BET method, scanning electron microscopy (SEM) and temperature programmed reduction (TPR). The XRD patterns revealed the NiO phase for all calcined catalysts. The chemical analysis confirmed the theoretical values of nickel. The catalysts were pre-treated under hydrogen at 500°C in situ, overnight before testing for the steam reforming of methane reaction (CH4/H2O/Ar = 10/10/80) in the temperature range (475°C - 650°C) under atmospheric pressure. The activities of both catalysts were investigated in a fixed-bed reactor for the Methane Steam Reforming (MSR) reaction. Globally, it was shown that the catalyst 10% nickel content has an important effect on the catalytic performances of solids i.e. the better results of hydrogen production were obtained with 10% wt. Ni/ZnO (28 ′ 10-3 mol/g catalyst).

Simultaneous syngas production with different H_2/CO ratio in a multi-tubular methane steam and dry reformer by utilizing of CLC

For syngas production, the combustion of fossil fuels produces large amounts of CO2 as a greenhouse gas annually which intensifies global warming. In this study, chemical looping combustion （CLC） has been utilized for the elimination of CO2 emission to atmosphere during simultaneous syngas production with different H2/CO ratio in steam reforming of methane （SR） and dry reforming of methane （DR） in a CLC-SR-DR configuration. In CLC-SR-DR with 184 reformer tubes （similar to an industrial scale steam reformer in Zagros Petrochemical Company, Assaluyeh, Iran）, DR reaction occurs over Rh-based catalysts in 31 tubes. Also, SR reaction is happened over Ni-based catalysts in 153 tubes. CLC via employment of Mn-based oxygen carriers supplies heat for DR and SR reactions and produces CO2 and H2O as raw materials simultaneously. A steady state heterogeneous catalytic reaction model is applied to analyze the performance and applicability of the proposed CLC-SR-DR configuration. Simulation results show that combustion efficiency reached 1 at the outlet of fuel reactor （FR）. Therefore, pure CO2 and H2O can be recycled to DR and SR sides, respectively. Also, CH4 conversion reached 0.2803 and 0.7275 at the outlet of SR and DR sides, respectively. Simulation results indicate that, 3223 kmol.h-l syngas with a H2/CO ratio equal to 9.826 was produced in SR side of CLC-SR-DR. After that, 1844 kmol.h-1 syngas with a H2/CO ratio equal to 0.986 was achieved in DR side of CLC-SR-DR. Results illustrate that by increasing the number of DR tubes to 50 tubes and considering 184 fixed total tubes in CLC-SR-DR, CH4 conversions in SR and DR sides decreased 2.69% and 3.31%, respectively. However, this subject caused total syngas production in SR and DR sides （in all of 184 tubes） enhance to 5427 kmol-h-1. Finally, thermal and molar behaviors of the proposed configuration demonstrate that CLC-SR-DR is applicable for simultaneous syngas production with high and low Hx/CO ratios in an environmental friendly process.

Life Cycle Assessment of Enriched Methane Produced by a Concentrated Solar Power Plant Coupled with a Steam Reforming Process

The global energy related challenges, mainly due to the worldwide growing energy consumption gone with a reduction ofoil and gas availability, is leading to an increasing interest on hydrogen as energy carrier. Molten salts at temperatures up to 550 ~C can be used as solar heat carrier and storage system, and hydrogen selective membranes can be used to drive reforming reaction at lower temperatures than conventional （〈 550 ~C）, with hydrogen purification achieved thereby. The combination of new technologies such as membranes and membrane reactors, concentrating solar power （CSP） systems and molten salt heat carriers, allows a partial decarbonation of the fossil fuel together with the possibility to carry solar energy in the current natural gas grid. The aim of this work is to present a life cycle assessment of a novel hybrid plant for the production of a mixture of methane and hydrogen, called enriched methane, from a steam reforming reactor whose heat duty is supplied by a molten salt stream heated up by an innovative concentrating solar power （CSP） plant developed by ENEA. The performance of this plant will be evaluated from an environmental point of view by the use of an LCA software （SimaPro7） and compared with the ones of traditional plants （reformer and cracker for the hydrogen production） for the production of enriched methane.

Profitability Analysis of Selected Steam Methane Reforming Methods for Hydrogen Production

One of the matured methods for producing hydrogen in bulk is steam methane reforming (SMR). The two commercial aspects of producing hydrogen from SMR are SMR with shift reactor (SR) and SMR with dry methane reforming (DRM). Although SMR with SR produces high hydrogen yield, it emits a large quantity of carbon dioxide (CO2). On the contrary, SMR and DRM produce low hydrogen yield but favorably emit a low quantity of CO2. However, it is not obvious which of these methods is more favourable economically. Consequently, using UNISIM Software Package, this study investigates three SMR methods namely SMR with SR, SMR with DRM and SMR with the combination of DRM and SR for the purpose of determining the most favourable route for producing hydrogen. This was done on the basis of feedstock rate of 100 kmol/hr of methane which reacted with 250 kmol/hr of steam for 8000 hrs annually using the rate of CO2 and CO emissions (COx) and the plant net profit percentage as performance indices. The profitability analysis shows that SMR/SR process is the most profitable process with a net profit percentage of 41.3%. Moreover, SMR/SR process has the highest yield and interestingly lowest COx emission rate. It is therefore concluded that the most favourable process route, technically and economically, is SMR/SR for the production of hydrogen using methane as feedstock.

Multi-Physics Modeling Assisted Design of Non-Coking Anode for Planar Solid Oxide Fuel Cell Fueled by Low Steam Methane

Internal reformation of low steam methane fuel is highly beneficial for improving the energy efficiency and reducing the system complexity and cost of solid oxide fuel cells(SOFCs).However,anode coking for the Ni-based anode should be prevented before the technology becomes a reality.A multi-physics fully coupled model is employed to simulate the operations of SOFCs fueled by low steam methane.The multi-physics model produces I-V relations that are in excellent agreement with the experimental results.The multi-physics model and the experimental non-coking current density deduced kinetic carbon activity criterion are used to examine the effect of operating parameters and the anode diffusion barrier layer on the propensity of carbon deposition.The interplays among the fuel utilization ratio,current generation,thickness of the barrier layer and the cell operating voltage are revealed.It is demonstrated that a barrier layer of 400μm thickness is an optimal and safe anode design to achieve high power density and non-coking operations.The anode structure design can be very useful for the development of high efficiency and low cost SOFC technology.

Efficiency analysis of sorption-enhanced method in steam methane reforming process

The sorption-enhanced method can change the thermodynamic equilibrium by absorbing CO_(2).However,it also brings about the problems of high regeneration temperature of adsorbent and large regeneration energy consumption.In order to study the impact of enhanced adsorption methods on the overall energy cost of the system in the hydrogen production process,this paper analyzes and compares steam methane reforming and reactive adsorption-enhanced steam methane reforming with the energy consumption of hydrogen production products as the evaluation index.The results showed that the energy consumption per unit hydrogen production decreased from 276.21 MJ/kmol to 131.51 MJ/kmol,and the decomposition rate of H2O increased by more than 20%after the addition of adsorption enhancement method.It is proved that the advantage of sorption enhanced method on pre-separation of CO_(2)in the product makes up for the disadvantage of energy consumption of adsorbent regeneration.In addition,the ability of the process to obtain H element is improved by the high decomposition rate of H2O,which realizes a more rational distribution of the element.

天然气-中温太阳能互补的新型低碳分布式供能系统

基于化学链循环的天然气-太阳能互补转化具有低碳、储能及高效等特点。目前甲烷化学链循环典型还原温度为800℃。在450℃中温条件下,现有技术的甲烷转化率均较低,导致热化学蓄能效率和分布式能源系统能效较低。基于产物分离促进反应平衡移动原理,提出将甲烷重整制氢与化学链循环结合的蓄能方法,氢气被载氧体消耗使氢气分压降低,促进甲烷重整反应正向进行,进而提升甲烷转化率。对比了甲烷重整耦合化学链循环蓄能方法和传统甲烷直接与载氧体发生化学链反应蓄能方法的甲烷转化率。结果表明,450℃下通过多级循环实现甲烷近完全转化。基于甲烷重整耦合化学链循环蓄能方法,建立了多能互补分布式供能系统模型,太阳能甲烷热化学源头蓄能将低品位太阳能提升为高品位燃料化学能,实现了源头蓄能与脱碳。储存太阳能的固体燃料氧化产生高温热能,通过透平做功发电,然后通过余热回收装置实现吸收式制冷和供热,从而实现太阳能和化石燃料的高效互补利用。对系统在典型工况下的热力学性能进行分析,结果表明基于甲烷重整耦合化学链循环蓄能方法的分布式供能系统太阳能净发电效率达24.90%,系统燃料节省率达43.24%,在节能减排方面具有显著优势。

KINETIC STUDY OF THE CATALYTIC STEAM REFORMING OF PARAFFINS

Kinetics of the steam reformig of n-butane,n-hexane,n-heptane,n-nonane and i-octane on Z409 catalystwere studied at atmospheric pressure by using an internal recycle gradientless reactor.The reaction temperaturewas varied in the range of 743-853K,the steam carbon molar ratio 3-5.The experimental results showed thatthe reforming products contained no hydrocarbon other than methane.In addition,the product distributionof different n-paraffins were similar,but the product distribution of i-octane was different from that of n-paraffins.A reaction scheme for the steam reforming of paraffin has been proposed and the hyperbolic type rateequations were derived.It is clear that the obtained kinetic model could simulate the experimental results ofi-octane as well as different n-paraffins satisfactorily.

Hydrogen and syngas production from two-step steam reforming of methane over CeO_2-Fe_2O_3 oxygen carrier

Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Renewable energy can be used to drive this process for hydrogen production, especially solar energy. CeO2-Fe2O3 complex oxide oxygen carrier was prepared by the impregnation method and characterized by means of X-ray diffractometer (XRD), Raman spectroscopy (Raman) and hydrogen programmed reduction (H2-TPR). CH4 temperature programmed and isothermal reactions were adopted to test syngas production reactivity, and water splitting reaction was employed to investigate water-splitting activity. Moreover, two-step SRM performance was evaluated by a successive redox cycle. The results showed that CO-uncontaminated H2 and highly selective syngas (with H2/CO ratio close to 2) could be respectively obtained from two steps, and CeFeO3 formation was found in the first redox cycle and proved to be enhanced by the redox treatment. After 10 successive cycles, obvious CeFeO3 phase was detected, which may be responsible for favorable successive redox cycle performances.

Multi-objective optimization for membrane reactor for steam methane reforming heated by molten salt

A membrane reactor for steam methane reforming heated by molten salt(MS-SMRMR)is studied based on finite time thermodynamics for decreasing carbon emissions and improving hydrogen production rate(HPR).Effects of flow directions of sweep gas and molten salt on MS-SMRMR are researched.Profiles of temperatures,HPR,and local entropy generation rates(EGRs)of MS-SMRMR are analyzed.Hybrid particle swarm optimization algorithm is utilized to obtain the minimum of specific EGR(SEGR),ratio of EGR to HPR.Multi-objective optimization about HPR maximization and EGR minimization is performed by utilizing NSGA-II.The EGR caused by the mass transfer process is the largest among all irreversible processes in the MS-SMRMR.The membrane length should be slightly shorter than the reactor length when the flow direction of sweep gas is different from that of reaction mixture.When flow directions of molten salt and sweep gas are opposite to that of reaction mixture,SEGR is the smallest.Compared with SEGR calculated by utilizing initial parameters,SEGRs after primary,twice and triple optimizations reduce by 1.2%,5.5%and 5.7%,respectively.SEGR can be further decreased by adjusting other operating parameters.Pareto front provides many optimization results,and it contains SEGR minimization.In Pareto front,an optimum decision point is obtained based on decision-making of TOPSIS,and its EGR and HPR,respectively,increase by 7.12%and13.24%,compared with those obtained by using initial parameters.The results have certain theoretical guiding significance for optimization designs of MS-SMRMR.