Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe_(2)O_(3)@SBA-16

To solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process.The decoupling strategy was adopted to decouple the biomass gasification process,and the composite oxygen carrier was prepared by embedding Fe_(2)O_(3) in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane,which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas.Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method,and the reforming performance was evaluated by a fixed bed reactor,and the kinetic parameters were solved based on the gas–solid reaction model.Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design.The experimental results showed that the reaction performance of Fe_(2)O_(3)@SBA-16 was compared with that of pure Fe_(2)O_(3) and Fe_(2)O_(3)@SBA-15,and the syngas yield was increased by 55.3%and 20.7%respectively,and it had good cycle stability.Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature.The activation energy was 192.79 kJ/mol by fitting.This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

Hydrogen production via chemical looping reforming of coke oven gas

Coke oven gas(COG)is one of the most important by-products in steel industry,and the conversion of COG to value-added products has attracted much attention from both economic and environmental views.In this work,we use the chemical looping reforming technology to produce pure H_(2) from COG.A series of La1-xSrxFeO_(3)(x?0,0.2,0.3,0.4,0.5,0.6)perovskite oxides were prepared as oxygen carriers for this purpose.The reduction behaviors of La1-xSrxFeO_(3) perovskite by different reducing gases(H_(2),CO,CH4 and the mixed gases)are investigated to discuss the competition effect of different components in COG for reacting with the oxygen carriers.The results show that reduction temperatures of H_(2) and CO are much lower than that of CH4,and high temperatures(>800℃)are requested for selective oxidation of methane to syngas.The co-existence of CO and H_(2) shows weak effect on the equilibrium of methane conversion at high temperatures,but the oxidation of methane to syngas can inhibit the consumption of CO and H_(2).The doping of suitable amounts of Sr in LaFeO_(3) perovskite(e.g.,La0.5Sr0.5FeO_(3))significantly promotes the activity for selective oxidation of methane to syngas and inhibits the formation of carbon deposition,obtaining both high methane conversion in the COG oxidation step and high hydrogen yield in the water splitting step.The La0.5Sr0.5FeO_(3) shows the highest methane conversion(67.82%),hydrogen yield(3.34 mmol g^(-1))and hydrogen purity(99.85%).The hydrogen yield in water splitting step is treble as high as the hydrogen consumption in reduction step.These results reveal that chemical looping reforming of COG to produce pure H_(2) is feasible,and an O_(2)-assistant chemical looping reforming process can further improves the redox stability of oxygen carrier.

Layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers for chemical looping reforming

A series of layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers were prepared for co-production of syngas and pure hydrogen via chemical looping steam reforming(CLSR).The presence of magnesium-aluminum layered double oxides(Mg Al-LDO)significantly increases the specific surface area of the mixed oxides,reduces the particle size of CeO2-based solid solution and promotes the dispersion of free Fe2O3.When reacting with methane,Mg Al-LDO supported oxygen carrier shows much lower temperature for methane oxidation than the pure CeFe-Zr-O sample,indicating enhanced low-temperature reactivity.Among different Ce-Fe-Zr-O(x)/Mg Al-LDO samples,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO sample shows the best performance for the selective oxidation of methane to syngas and the H2 production by water splitting.After a long period of high temperature redox experiment,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier still shows high activity for syngas generation.The comparison on the morphology of the fresh and cycled oxygen carriers indicates that the Mg-Al spinel support still forms a stable skeleton structure with high dispersion of active components on the surface after the long-term cycling,which contributes to excellent redox stability of the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier.

Syngas production from chemical looping reforming of ethanol over iron-based oxygen carriers: Theoretical analysis and experimental investigation

Chemical looping reforming(CLR)is a recent trend for syngas production,which has several merits compared to the conventional manner.One of the most important issues for CLR is to find low-cost material as oxygen carriers,so iron is a promising candidate.This paper contributes to testing the thermodynamic ability of iron-based oxygen carrier for chemical looping reforming of ethanol(CLRE).Iron thermodynamically investigated in temperature 100–1300℃and excess oxygen number(φ)0–4.It was found that the temperature andφhave an apparent effect on the gaseous composition produced from the process.Increases in temperature within the range of 100–1300℃enhanced syngas generated and reduced coke formation and CH4.Whereas,increasedφ,particularly at higher temperatures,had also enhanced syngas production as well as reduced coke formation.However,increasingφfor values beyond one had decreased syngas and not significantly reduced coke deposition.Moreover,an experimental investigation was carried out in a fixed bed reactor for more in-depth verification of iron ability as an oxygen carrier through using magnetite ore(mainly Fe3O4).It found that the effect of temperature on syngas production was consistent with that calculated thermodynamically,as syngas increased with raising the temperature through the CLRE.

Optimizing the sulfur-resistance and activity of perovskite oxygen carrier for chemical looping dry reforming of methane

Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.

Reduction kinetics of SrFeO_(3−δ)/CaO∙MnO nanocomposite as effective oxygen carrier for chemical looping partial oxidation of methane

Chemical looping reforming of methane is a novel and effective approach to convert methane to syngas,in which oxygen transfer is achieved by a redox material.Although lots of efforts have been made to develop high-performance redox materials,a few studies have focused on the redox kinetics.In this work,the kinetics of SrFeO_(3−δ)–CaO∙MnO nanocomposite reduction by methane was investigated both on a thermo-gravimetric analyzer and in a packed-bed microreactor.During the methane reduction,combustion occurs before the partial oxidation and there exists a transition between them.The weight loss due to combustion increases,but the transition region becomes less inconspicuous as the reduction temperature increased.The weight loss associated with the partial oxidation is much larger than that with combustion.The rate of weight loss related to the partial oxidation is well fitted by the Avrami–Erofeyev equation with n=3(A3 model)with an activation energy of 59.8 kJ∙mol^(‒1).The rate law for the partial oxidation includes a solid conversion term whose expression is given by the A3 model and a methane pressure-dependent term represented by a power law.The partial oxidation is half order with respect to methane pressure.The proposed rate law could well predict the reduction kinetics;thus,it may be used to design and/or analyze a chemical looping reforming reactor.