Steam carbon gasification of a nickel based oxygen carrier

Ni-based oxygen carriers are promising candidates for Chemical Looping applications due to a combination of excellent methane conversion performance, mechanical stability, oxygen transfer capacity. However, experiments conducted on NiO/NiAl₂O₄ in a micro-fluidized bed reactor show that methane forms coke on active nickel sites. In subsequent tests, water vapour was fed to the coked Ni oxygen carrier producing a highly concentrated stream of CO/H₂ (1/1). In the absence of water vapour, production of hydrogen dropped with time while a methane/argon mixture was fed to the reactor. Co-feeding water together with methane improves stability - both H₂ production and carbon deposition were constant for over 1 h. Despite the tremendous lay down of carbon, catalytic activity remained stable at levels as low as 3 vol.% water vapour (and 10% methane). Water vapour is an effective oxidant for Ni(0) but is insufficient to entirely re-oxidize the oxygen carrier from Ni to NiO.     

CO2 reforming of CH4 in coke oven gas to syngas over coal char catalyst

The CO₂ reforming of methane (in coke oven gas) on the coal char catalyst was performed in a fixed bed reactor at temperatures between 800 and 1200 °C under normal pressure. The effects of the coal char catalyst pretreatment and the ratio of CO₂/CH₄ were studied. Experimental results showed that the coal char was an effective catalyst for production of syngas, and addition of CO₂ did not enhance the CH₄ reforming to H₂. It was also found that the product gas ratio of H₂/CO is strongly influenced by the feed ratio of CO₂/CH₄. The modified coal char catalyst was more active during the CO₂–CH₄ reforming than the coal char catalyst based on the catalyst volume, furthermore the modified catalyst exhibited high activity in CO₂–CH₄ reforming to syngas. The conversion of methane can be divided into two stages. In the first stage, the conversion of CH₄ gradually decreased. In the second stage, the conversion of methane maintained nearly constant. The conversion of CO₂ decreased slightly during the overall reactions in CO₂–CH₄ reforming. The coal char catalyst is a highly promising catalyst for the CO₂ reforming of methane to syngas.     

Methane oxidation on the surface of mixed-conducting La0.3Sr0.7Co0.8Ga0.2O3-δ

Mixed-conducting La_0.3Sr_0.7Co_0.8Ga_0.2O_3-δ (LSCG) possesses substantial oxygen permeability, but exhibits a high activity to complete CH₄ oxidation, thus making it necessary to incorporate reforming catalysts in the membrane reactors for methane conversion. Dominant CO₂ formation is observed for the steady-state conversion of CH₄ by atmospheric oxygen (methane/air ratio of 30:70) in a fixed bed reactor with LSCG as catalyst, and for the oxidation of CH₄ pulses supplied in helium flow over LSCG powder. The conversion of dry CH₄ by oxygen permeating through dense LSCG ceramics, stable operation of which under the air/CH₄ gradient is possible due to the surface-limited oxygen transport, yields CO₂ concentrations higher than 90%. The prevailing mechanism of total methane combustion is probably associated with weak Co–O bonding in the perovskite-related LSCG lattice, in correlation with data on oxygen desorption, phase stability and ionic transport.     

Numerical simulation of particle/monolithic two-stage catalyst bed reactor with beds-interspace distributed dioxygen feeding for oxidative coupling of methane

A three-dimensional geometry model of the particle/monolithic two-stage reactor with beds-interspace distributed dioxygen feeding for oxidative coupling of methane (OCM) was set up. The improved Stansch kinetic model adapting different operating temperatures was established to calculate the OCM reactor performance using computational fluid dynamics (CFD) and FLUENT software. The results showed that the calculated values matched well with the experimental values of the conversion of CH₄ and the selectivity of products (C₂H₆, C₂H₄, CO₂, CO) in the OCM reactor. The distributed dioxygen feeding with the percentage of 5–20% based oxygen flow rate of top inlet promoted the OCM reaction in monolithic catalyst bed and led to the conversion of CH₄ and the selectivity and yield of C₂ (C₂H₆ and C₂H₄) increase obviously. The distributed dioxygen feeding was 15%, the conversion of CH₄, the selectivity and the yield of C₂ reached 34.1%, 68.2% and 23.3%, respectively.     

The reaction of NiO/NiAl2O4 particles with alternating methane and oxygen

The reduction and oxidation behaviour of oxygen carrier particles of NiO and NiAl₂O₄ has been investigated in a fluidized bed reactor as well as a thermogravimetric analyzer (TGA). The particles showed high reactivity and gas yield to CO₂ with methane in the temperature interval 750–950°C. In the fluidized bed the yield to CO₂ was between 90 and 99% using bed masses corresponding to 16–57 kg/MW_fuel. Complementary experiments in a TGA at 750 and 950°C showed a clear reaction of the NiAl₂O₄ with CH₄ at the higher temperature. There was methane released from the reactor at high degrees of solid oxidation, which is likely associated with the lack of Ni‐sites on the particles which can reform the methane. There was some carbon formation during the reduction, although the amount was minor when the gas yield to carbon dioxide and degree of oxidation of the solid was high. A simple reactor model using kinetic data from a previous study predicted the gas yield during the reduction in the fluidized bed experiments with reasonable accuracy. The oxygen carrier system investigated in this work shows high promise for use in a real CLC system, provided that the particle manufacturing process can be scaled up with reasonable cost.     

The use of NiO as an oxygen carrier in chemical-looping combustion

The feasibility of using NiO as an oxygen carrier during chemical-looping combustion has been investigated. A thermodynamic analysis with CH₄ as fuel showed that the yield of CH₄ to CO₂ and H₂O was between 97.7 and 99.8% in the temperature range 700–1200 °C, with the yield decreasing as the temperature increases. Carbon deposition is not expected as long as sufficient metal oxide is supplied to the fuel reactor. Hydrogen sulfide, H₂S, in the fuel gas will be converted partially to SO₂ in the gas phase, with the degree of conversion increasing with temperature, but decreasing as a function of pressure. There is the possibility of sulfide formation as Ni₃S₂ at higher partial pressures of H₂S+SO₂ in the reactor. The reactivity of freeze granulated particles of NiO with NiAl₂O_4, MgAl₂O₄, TiO₂ and ZrO₂ sintered at different temperatures was investigated in a small fluidized bed reactor by exposing them cyclically to 50% CH₄/50% H₂O and 5% O₂ at 950 °C. During the reducing period, the NiO initially reacted with the CH₄ to form CO₂ and H₂O. However, there were always minor amounts of CO from the outlet of the reactor even at high concentrations of CO₂, which was due to the thermodynamic limitations. Here, the ratio CO/(CO₂+CO+CH₄) was between 1.5 and 2.5% at 950 °C for the oxygen carriers with alumina based inert. A small amount of CH₄ was released from the reactor at high degrees of oxidation of the NiAl₂O₄ and MgAl₂O₄-based carriers. As the time under reducing conditions increased, steam reforming of CH₄ to CO and H₂ became considerable, with Ni catalyzing this reaction. Whereas the ZrO₂ particles showed similar behavior as the alumina-based carriers, the TiO₂-based particles showed a markedly different reaction behavior, likely due to the complex interaction between NiO and TiO₂.     

Autothermal Reforming of Methane with Integrated CO2 Capture in a Novel Fluidized Bed Membrane Reactor. Part 1: Experimental Demonstration

Two fluidized bed membrane reactor concepts for hydrogen production via autothermal reforming of methane with integrated CO₂ capture are proposed. Ultra-pure hydrogen is obtained via hydrogen perm-selective Pd-based membranes, while the required reaction energy is supplied by oxidizing part of the CH₄ in situ in the methane combustion configuration or by combusting part of the permeated H₂ in the hydrogen combustion configuration (oxidative sweeping). In this first part, the technical feasibility of the two concepts has been studied experimentally, investigating the reactor performance (CH₄ conversion, CO selectivity, H₂ production and H₂ yield) at different operating conditions. A more detailed comparison of the performance of the two proposed reactor concepts is carried out with a simulation study and is presented in the second part of this work.     

Simultaneous oxidative conversion and CO2 or steam reforming of methane to syngas over CoO–NiO–MgO catalyst

CO₂ reforming, oxidative conversion and simultaneous oxidative conversion and CO₂ or steam reforming of methane to syngas (CO and H₂) over NiO–CoO–MgO (Co: Ni: Mg=0·5: 0·5:1·0) solid solution at 700–850°C and high space velocity (5·1×10⁵ cm³ g⁻¹ h⁻¹ for oxidative conversion and 4·5×10⁴ cm³ g⁻¹ h⁻¹ for oxy-steam or oxy-CO₂ reforming) for different CH₄/O₂ (1·8–8·0) and CH₄/CO₂ or H₂O (1·5–8·4) ratios have been thoroughly investigated. Because of the replacement of 50 mol% of the NiO by CoO in NiO–MgO (Ni/Mg=1·0), the performance of the catalyst in the methane to syngas conversion process is improved; the carbon formation on the catalyst is drastically reduced. The CoO–NiO–MgO catalyst shows high methane conversion activity (methane conversion >80%) and high selectivity for both CO and H₂ in the oxy-CO₂ reforming and oxy-steam reforming processes at ⩾800°C. The oxy-steam or CO₂ reforming process involves the coupling of the exothermic oxidative conversion and endothermic CO₂ or steam reforming reactions, making these processes highly energy efficient and also safe to operate. These processes can be made thermoneutral or mildly exothermic or mildly endothermic by manipulating the process conditions (viz. temperature and/or CH₄/O₂ ratio in the feed). © 1998 Society of Chemistry Industry     

Catalytic partial oxidation of CH4 over bimetallic Ni‐Re/Al2O3: Kinetic determination for application in microreactor

The activity of a novel Ni‐Re/Al₂O₃ catalyst toward partial oxidation of methane was investigated in comparison with that of a precious‐metal Rh/Al₂O₃ catalyst. Reactions involving CH₄/O₂/Ar, CH₄/H₂O/Ar, CH₄/CO₂/Ar, CO/O₂/Ar, and H₂/O₂/Ar were performed to determine the kinetic expressions based on indirect partial oxidation scheme. A mathematical model comprising of Ergun equation as well as mass and energy balances with lumped indirect partial oxidation network was applied to obtain the kinetic parameters and then used to predict the reactant and product concentrations as well as temperature profiles within a fixed‐bed microreactor. H₂ and CO production as well as H₂/CO₂ and CO/CO₂ ratios from the reaction over Ni‐Re/Al₂O₃ catalyst were higher than those over Rh/Al₂O₃ catalyst. Simulation revealed that much smoother temperature profiles along the microreactor length were obtained when using Ni‐Re/Al₂O₃ catalyst. Steep hot‐spot temperature gradients, particularly at the entrance of the reactor, were, conversely, noted when using Rh/Al₂O₃ catalyst. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1691–1701, 2018     

基于NiO载氧体的煤化学链燃烧实验

采用流化床反应器并以水蒸气作为气化-流化介质,研究了以NiO为载氧体在800～960℃内的煤化学链燃烧反应特性。实验结果表明,载氧体与煤气化产物在反应器温度高于900℃体现了高的反应活性。随着流化床反应器温度的提高,气体产物中CO₂的体积浓度(干基)呈单调递增;CO、H₂、CH₄的体积浓度(干基)呈单调递减;煤中碳转化为CO₂的比率逐渐递增,碳的残余率逐渐递减。反应器出口气体CO₂、CO、H₂、CH₄的生成率随反应时间呈单峰特性,H₂生成率的峰值远小于CO的峰值;且随反应器温度升高,CO₂生成率升高,CO、H₂、CH₄的生成率降低。反应温度高于900℃时,流化床反应器NiO载氧体煤化学链燃烧在9 min之内就基本完成,CO₂含量高于92%。     

Effective methane reforming with CO2 and O2 under pressurized condition using NiO–MgO and fluidized bed reactor

Circulation of Ni_0.15Mg_0.85O catalyst particles in the fluidized bed reactor gave much higher CH₄ conversion in methane reforming with CO₂ and O₂ under pressurized condition than the case of the catalyst without moving in the fixed bed reactor. In addition, circulation of the catalyst particles in the fluidized bed reactor inhibited carbon deposition which is the serious problem in methane reforming.     

Co-generation of synthesis gas and C2+ hydrocarbons from methane and carbon dioxide in a hybrid catalytic-plasma reactor: A review

The topics on conversion and utilization of methane and carbon dioxide are important issues in tackling the global warming effects from the two greenhouse gases. Several technologies including catalytic and plasma have been proposed to improve the process involving conversion and utilization of methane and carbon dioxide. In this paper, an overview of the basic principles, and the effects of CH₄/CO₂ feed ratio, total feed flow rate, discharge power, catalyst, applied voltage, wall temperature, and system pressure in dielectric-barrier discharge (DBD) plasma reactor are addressed. The discharge power, discharge gap, applied voltage and CH₄/CO₂ ratio in the feed showed the most significant effects on the reactor performance. Co-feeding carbon dioxide with the methane feed stream reduced coking and increased methane conversion. The H₂/CO ratio in the products was significantly affected by CH₄/CO₂ ratio. The synergism of the catalyst placed in the discharge gap and the plasma affected the products distribution significantly. Methane and carbon dioxide conversions were influenced significantly by discharge power and applied voltage. The drawbacks of DBD plasma application in the CH₄–CO₂ conversion should be taken into consideration before a new plausible reactor system can be implemented.     

Autothermal Reforming of Methane with Integrated CO2 Capture in a Novel Fluidized Bed Membrane Reactor. Part 2 Comparison of Reactor Configurations

The reactor performance of two novel fluidized bed membrane reactor configurations for hydrogen production with integrated CO₂ capture by autothermal reforming of methane (experimentally investigated in Part 1) have been compared using a phenomenological reactor model over a wide range of operating conditions (temperature, pressure, H₂O/CH₄ ratio and membrane area). It was found that the methane combustion configuration (where part of the CH₄ is combusted in situ with pure O₂) largely outperforms the hydrogen combustion concept (oxidative sweeping combusting part of the permeated H₂) at low H₂O/CH₄ ratios (<2) due to in situ steam production, but gives a slightly lower hydrogen production rate at higher H₂O/CH₄ ratios due to dilution with combustion products. The CO selectivity was always much lower with the methane combustion configuration. Whether the methane combustion or hydrogen combustion configuration is preferred depends strongly on the economics associated with the H₂O/CH₄ ratio.     

Carbon deposition characteristics and regenerative ability of oxygen carrier particles for chemical-looping combustion

For gaseous fuel combustion with inherent CO₂ capture and low NO_x emission, chemical-looping combustion (CLC) may yield great advantages for the savings of energy to CO₂ separation and suppressing the effect on the environment. In a chemical-looping combustor, fuel is oxidized by metal oxide medium (oxygen carrier particle) in a reduction reactor. Reduced particles are transported to the oxidation reactor and oxidized by air and recycled to the reduction reactor. The fuel and the air are never mixed, and the gases from the reduction reactor, CO₂ and H₂O, leave the system as separate streams. The H₂O can be easily separated by condensation and pure CO₂ is obtained without any loss of energy for separation. In this study, NiO based particles are examined from the viewpoints of reaction kinetics, carbon deposition, and cyclic use (regenerative ability). The purpose of this study is to find appropriate reaction conditions to avoid carbon deposition and achieve high reaction rate (e.g., temperature and maximum carbon deposition-free conversion) and to certify regenerative ability of NiO/bentonite particles. In this study, 5.04% methane was used as fuel and air was used as oxidation gas. The carbon deposition characteristics, reduction kinetics and regenerative ability of oxygen carrier particles were examined by TGA (Thermal Gravimetrical Analyzer).     

Catalytic decomposition of methane over a wood char concurrently activated by a pyrolysis gas

The catalytic activity of a wood char towards CH₄ decomposition in a pyrolysis gas was investigated in a fixed bed reactor for maximising hydrogen production from biomass gasification. Wood char is suggested to be the cheapest and greenest catalyst for CH₄ conversion as it is directly produced in the pyrolysis facility. The conversion of methane reaches 70% for a contact time of 120 ms at 1000 °C. Because steam and CO₂ are simultaneously present in the pyrolysis gas, the carbon catalyst is continuously regenerated. Hence the conversion of methane quickly stabilises. Such a phenomenon is shown to be possible through the oxidation of the char by CO₂ and H₂O at high temperature, which prevents the blocking of the mouth of pores by the concurrent pyrolytic carbon deposition. In the experimental conditions, oxygenated functional surface groups are continuously formed (by steam and CO₂ oxidation) and thermally decomposed. The active sites for CH₄ chemisorption and decomposition are suggested to be the unsaturated carbon atoms generated by the evolution of the oxygenated functions at high temperature.     

Efficient synthesis of ethanol and acetic acid from methane and carbon dioxide with a continuous,stepwise reactor

The synthesis of C₂‐oxygenates such as ethanol and acetic acid accomplished by CH₄ dissociation and subsequent CO₂ insertion onto methyl radicals, named the stepwise reaction technology, has been demonstrated to be both feasible and efficient through initial experiments conducted in microreactor units. This article describes the development of this technology, highlighting the aforementioned stepwise technology using a dual‐reactor system, which can ensure that two raw gases enter the reactor uninterruptedly and are not mixed after reaction. The system productivity for acetic acid and ethanol displayed efficiencies greater than 5–10 times that of previous microreactor units. The investigation of mechanism indicates that acetic acid arises from insertion of CO₂ into M? CH_x, while ethanol is formed either by hydrogenation of acetic acid or by hydration of C₂H₄, which results from homo‐coupling of CH₄. The latter route is the preferred of the two. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Higher Hydrocarbon Production through Oxidative Coupling of Methane Combined with Hydrogenation of Carbon Oxides

In the production of higher hydrocarbons, combining oxidative coupling of methane (OCM) with hydrogenation of the formed carbon oxides in a separate reactor provides an alternative to the currently applied methane conversion to syngas followed by Fischer‐Tropsch synthesis. The effects of CH₄:O₂ feed ratio in the OCM reactor and partial pressures of H₂ or/and H₂O in the hydrogenation reactor were analyzed to maximize production of C₂₊ hydrocarbons and reduce CO_x formation. The highest C₂₊ yield was achieved with low CH₄:O₂ feed ratio for OCM and removal of the formed water before entering the hydrogenation reactor.     

Effect of temperature on reduction reactivity of oxygen carrier particles in a fixed bed chemical-looping combustor

In a chemical-looping combustor (CLC), gaseous fuel is oxidized by metal oxide particle, e.g. oxygen carrier, in a reduction reactor (combustor), and the greenhouse gas CO₂ is separated from the exhaust gases during the combustion. In this study, NiO/bentonite particle was examined on the basis of reduction reactivity, carbon deposition during reduction, and NO_x formation during oxidation. Reactivity data for NiO/bentonite particle with methane and air were presented and discussed. During the reduction period, most of the CH₄ are converted to CO₂ with small formation of CO. Reduction reactivity (duration of reduction) of the NiO/bentonite particle increased with temperature, but at higher temperature, it is somewhat decreased. The NiO/bentonite particle tested showed no agglomeration or breakage up to 900 ‡C, but at 1,000 ‡C, sintering took place and lumps of particles were formed. Solid carbon was deposited on the oxygen carrier during high conversion region of reduction, i.e., during the end of reduction. It was found that the appropriate temperature for the NiO/bentonite particle is 900 ‡C for carbon deposition, reaction rate, and duration of reduction. We observed experimentally that NO, NO₂, and N₂O gases are not generated during oxidation.     

Using continuous and pulse experiments to compare two promising nickel-based oxygen carriers for use in chemical-looping technologies

Chemical-looping technologies have obtained widespread recognition as power or hydrogen production units with inherent carbon capture in a future scenario where CO₂ capture and storage (CCS) is reality. In this paper three different techniques are described; chemical-looping combustion and two categories of chemical-looping reforming. The three techniques are all based on oxygen carriers that are circulating between an air- and a fuel reactor, providing the fuel with undiluted oxygen. Two different oxygen carriers; NiO/NiAl₂O₄ (40/60 wt/wt) and NiO/MgAl₂O₄ (60/40 wt/wt) are compared. Both continuous and pulse experiments were performed in a batch laboratory fluidized bed working at 950 °C using methane as fuel. It was found that pulse experiments offer advantages in comparison to continuous experiments, particularly when evaluating suitable particles for autothermal chemical-looping reforming. Firstly, smaller conversion ranges can be investigated in more detail, and secondly, the onset and extent of carbon formation can be determined more accurately. Of the two oxygen carriers, NiO/MgAl₂O₄ offers several advantages at elevated temperatures, i.e. higher methane conversion, higher selectivity to reforming and lesser tendency for carbon formation.     

Reactivity of a CaSO<Subscript>4</Subscript>-oxygen carrier in chemical-looping combustion of methane in a fixed bed reactor

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. A reactivity study of CaSO₄ oxygen carrier in CLC of methane was conducted in a laboratory scale fixed bed reactor. The oxygen carrier particles were exposed in six cycles of alternating reduction methane and oxidation air. A majority of CH₄ reacted with CaSO₄ to form CO₂ and H₂O. The oxidation was incomplete, possibly due to the CaSO₄ product layer. The reactivity of CaSO₄ oxygen carrier increased for the initial cycles but slightly decreased after four cycles. The product gas yields of CO₂, CH₄, and CO with cycles were analyzed. Carbon deposition during the reduction period was confirmed with the combustible gas (CO+H₂) in the product gas and slight CO₂ formed during the early stage of oxidation. The mechanism of carbon deposition and effect was also discussed. SO₂ release behavior during reduction and oxidation was investigated, and the possible formation mechanism and mitigation method was discussed. The oxygen carrier conversion after the reduction decreased gradually in the cyclic test while it could not restore its oxygen capacity after the oxidation. The mass-based reaction rates during the reduction and oxidation also demonstrated the variation of reactivity of CaSO₄ oxygen carrier. XRD analysis illustrated the phase change of CaSO₄ oxygen carrier. CaS was the main reduction product, while a slight amount of CaO also formed in the cyclic test. ESEM analysis demonstrated the surface change of particles during the cyclic test. The reacted particles tested in the fixed bed reactor were not uniform in porosity. EDS analysis demonstrated the transfer of oxygen from CaSO₄ to fuel gas while leaving CaS as the dominant reduced product. The results show that CaSO₄ oxygen carrier may be an interesting candidate for oxygen carrier in CLC. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.