Auto-thermal reforming of acetic acid for hydrogen production by Zn_(x)Ni_(y)CrO_(m±δ) catalysts:Effect of Cr promoted Ni-Zn intermetallic compound

A series of Zn_(x)Ni_(y)CrO_(m±δ)catalysts were synthesized via a typical co-precipitation method,in which Zn-Cr layered double hydroxides(LDHs)were found and Ni-Zn intermetallic compound(IMC)was formed after reduction in hydrogen.During auto-thermal reforming(ATR)of acetic acid(HAc),the Ni-Zn IMC was transformed into Ni/(amorphous-ZnO)-ZnCr_(2)O_(4) species with uniformed distribution and appropriate interaction within these Ni-Zn-Cr-O species;besides,the adsorbed oxygen promoted the activation and transfer of oxygen species;therefore,deactivation by oxidation,sintering and coking was inhibited.And the optimized Zn_(2.37)Ni_(0.63)CrO_(4.5±δ)catalyst presented high activity and stability in a 45-h ATR test with HAc conversion near 100%and hydrogen yield at 2.7 mol-H_(2)/mol-HAc,showing potential for hydrogen production via ATR of HAc.

Upcycling municipal solid waste to sustainable hydrogen via two-stage gasification-reforming

As global municipal solid waste(MSW)quantities continue to escalate,serious socio-environmental challenges arise,necessitating innovative solutions.Waste-to-hydrogen(WTH)via two-stage gasification-reforming(TSGR)presents an emergent technology for MSW upcycling,offering to ease waste management burdens and bolster the burgeoning hydrogen economy.Despite early initiatives to advance TSGR technology,a cohesive and critical analysis of cutting-edge knowledge and strategies to enhance hydrogen production remains lacking.This review aggregates literature on MSW upcycling to hydrogen via TSGR,with a focus on optimizing process control and catalytic efficiency.It underscores technological avenues to augment hydrogen output,curtail catalyst costs,and refine system performance.Particularly,the review illuminates the potential for integrating chemical and calcium looping into TSGR processes,identifying opportunities,and pinpointing challenges.The review concludes with a summary of the current state of techno-economic analysis for this technology,presenting outstanding challenges and future research directions,with the ultimate goal of transitioning WTH from theoretical to practical application.

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.

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.

Machine learning-driven optimization of plasma-catalytic dry reforming of methane

This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimize the plasma-catalytic DRM reaction with limited experimental data.To address the non-linear and complex nature of the plasma-catalytic DRM process,the hybrid ML model integrates three well-established algorithms:regression trees,support vector regression,and artificial neural networks.A genetic algorithm(GA)is then used to optimize the hyperparameters of each algorithm within the hybrid ML model.The ML model achieved excellent agreement with the experimental data,demonstrating its efficacy in accurately predicting and optimizing the DRM process.The model was subsequently used to investigate the impact of various operating parameters on the plasma-catalytic DRM performance.We found that the optimal discharge power(20 W),CO_(2)/CH_(4)molar ratio(1.5),and Ni loading(7.8 wt%)resulted in the maximum energy yield at a total flow rate of∼51 mL/min.Furthermore,we investigated the relative significance of each operating parameter on the performance of the plasma-catalytic DRM process.The results show that the total flow rate had the greatest influence on the conversion,with a significance exceeding 35%for each output,while the Ni loading had the least impact on the overall reaction performance.This hybrid model demonstrates a remarkable ability to extract valuable insights from limited datasets,enabling the development and optimization of more efficient and selective plasma-catalytic chemical processes.

Engineering oxygen vacancies on Tb-doped ceria supported Pt catalyst for hydrogen production through steam reforming of long-chain hydrocarbon fuels

Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.

Ethanol steam reforming over Ni/ZSM-5 nanosheet for hydrogen production

Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the catalyst design strategies for preparing the Ni supported on ZSM-5 zeolite catalysts to promote ESR.Specifically,two-dimensional ZSM-5 nanosheet and conventional ZSM-5 crystal were used as the catalyst carriers and two synthesis strategies,i.e.,in situ encapsulation and wet impregnation method,were employed to prepare the catalysts.Based on the comparative characterization of the catalysts and comparative catalytic assessments,it was found that the combination of the in situ encapsulation synthesis and the ZSM-5 nanosheet carrier was the effective strategy to develop catalysts for promoting H_(2) production via ESR due to the improved mass transfer(through the 2-D structure of ZSM-5 nanosheet)and formation of confined small Ni nanoparticles(resulted via the in situ encapsulation synthesis).In addition,the resulting ZSM-5 nanosheet supported Ni catalyst also showed high Ni dispersion and high accessibility to Ni sites by the reactants,being able to improve the activity and stability of catalysts and suppress metal sintering and coking during ESR at high reaction temperatures.Thus,the Ni supported on ZSM-5 nanosheet catalyst prepared by encapsulation showed the stable performance with~88% ethanol conversion and~65% H_(2) yield achieved during a 48-h longevity test at 550-C.

Steam reforming of acetic acid over Ni/biochar of low metal-loading:Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.

Pt nanoclusters modified porous g-C_(3)N_(4)nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Dynamic Model Study and Analysis of DME Auto-Thermal Steam Reforming Reaction

Through the study of the kinetics of dimethyl ether steam reforming reaction, a two-dimensional model of the reactor is established. At the same time, rate equations of simplified elementary reactions of DME steam reforming reaction are deduced by the mechanism of Langmuir-Hinshel-wood, and the rate constants are obtained by correcting the pre-exponential factor of Arrhenius equation. Finally, the analog data of DME steam reforming reaction under a variety of conditions are obtained, and making a simulation diagram. The two-dimensional model is substantially correct because of the analog data more in line with a variety of knowledge.

High H_(2) selective performance of Ni-Fe-Ca/H-Al catalysts for steam reforming of biomass and plastic

The development of a selective catalyst for the conversion of biomass and plastics into H2by steam reforming can combat the energy crisis and global warming.In this work,support Ni-Fe-Ca/H-Al bifunctional catalysts were prepared by loading Ni and Fe into pretreatment CaO/Al_(2)O_(3)(Ca/H-Al)carriers and showed high catalytic activity for the steam reforming of biomass and plastic.Moreover,the idea of bidirectional degradation was exploited to strengthen the pyrolysis of plastic with a high H/C and biomass with a high O/C.Interestingly,the products presented high H2selective(1302.10 m L/g)and low CO_(2)yield(120.23 m L/g)in 7Ni-5Fe-Ca/H-Al(2:4)catalyst compared with current reports.Here,the abundant oxygen vacancies(Ov)in the H-Al carrier exhibited an electron-deficient nature,providing active sites for anchoring Ni O.Meanwhile,Ni O interacted with Ca_(2)Fe_(2)O_(5)to produce more defective Ovsites,which stabilized the NiO particles in the 7Ni-5Fe-Ca/H-Al(2:4)catalyst,and the interaction between the catalyst and the carrier was enhanced,leading to the reduction of weakly basic sites,this property promoted the strong adsorption of CO_(2)and H2O by the catalyst,contributing to the enhancement of efficient steam conversion and the promotion of conversion of by-products to H2.Notably,7Ni-5Fe-Ca/H-Al(2:4)catalysts maintained structural integrity after regeneration and exhibited excellent regenerability in H2selection and CO_(2)adsorption.The work provides a new idea for the study of efficient H2production from steam reforming of biomass and plastics.

Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model

Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO_(2)at Low Temperatures in Tahe Heavy Oil

MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.

The Nature of Active Sites for Plasmon-Mediated Photothermal Catalysis and Heat-Coupled Photocatalysis in Dry Reforming of Methane

Solar energy-induced catalysis has been attracting intensive interests and its quantum efficiencies in plasmon-mediated photothermal catalysis(P-photothermal catalysis)and external heat-coupled photocatalysis(E-photothermal catalysis)are ultimately determined by the catalyst structure for photo-induced energetic hot carriers.Herein,different catalysts of supported(TiO_(2)-P25 and Al_(2)O_(3))platinum quantum dots are employed in photo,thermal,and photothermal catalytic dry reforming of methane.Integrated experimental and computational results unveil different active sites(hot zones)on the two catalysts for photo,thermal,and photothermal catalysis.The hot zones of P-photothermal catalysis are identified to be the metal-support interface on Pt/P25 and the Pt surface on Pt/Al_(2)O_(3),respectively.However,a change of the active site to the Pt surface on Pt/P25 is for the first time observed in E-photothermal catalysis(external heating temperature of 700℃).The hot zones contribute to the significant enhancements in photothermal catalytic reactivity against thermocatalysis.This study helps to understand the reaction mechanism of photothermal catalysis to exploit efficient catalysts for solar energy utilization and fossil fuels upgrading.

Improvement strategies for Ni-based alcohol steam reforming catalysts

Steam reforming(SR)of fossil methane is already a well-known,documented and established expertise in the industrial sector as it accounts for the vast majority of global hydrogen production.From a sustainable development perspective,hydrogen production by SR of biomass-derived feedstock represents a promising alternative that could help to lower the carbon footprint of the traditional process.In this regard,bio-alcohols such as methanol,ethanol or glycerol are among the attractive candidates that could serve as green hydrogen carriers as they decompose at relatively low temperatures in the presence of water compared to methane,allowing for improved H_(2)yields.However,significant challenges remain regarding the activity and stability of nickel-based catalysts,which are most widely used in alcohol SR processes due to their affordability and ability to break C–C,O–H and C–H bonds,yet are prone to rapid deactivation primarily caused by coke deposition and metal particle sintering.In this state-of-the-art review,a portfolio of strategies to improve the performance of Ni-based catalysts used in alcohol SR processes is unfolded with the intent of pinpointing the critical issues in catalyst development.Close examination of the literature reveals that the efforts tackling these recurring issues can be directed at the active metal,either by tuning Ni dispersion and Ni-support interactions or by targeting synergistic effects in bimetallic systems,while others focus on the support,either by modifying acid-base character,oxygen mobility,or by embedding Ni in specific crystallographic structures.This review provides a very useful tool to orient future work in catalyst development.

An Energy Production System Powered by Solar Heat with Biogas Dry Reforming Reactor and Solid Oxide Fuel Cell

In this paper, an energy system consisting of solar collector, biogas dry reforming reactor and solid oxide fuel cell (SOFC) has been proposed. The heat produced from the concentrating solar collector is used to drive a biogas dry reforming reactor in order to produce H2 as a fuel for SOFC, in such as system. The aim of this study is to clarify the impact of climate data on the performance of solar collector with various sizes/designs. The temperature of heat transfer fluid produced by the solar collector is calculated by adopting the climate data for Nagoya city in Japan in 2021. The amount of H2 produced from the biogas dry reforming reactor and the power generated by SOFC were simulated. The results show the temperature of heat transfer fluid (Tfb) and Tfb ratio (a) based on the length of absorber (dx) = 1 m have a peak near the noon following the trend of solar intensity (I). Results also revealed that a increases with increase in dx. It is found that the differences of Tfb and a between dx = 2 m and dx = 3 m are larger than those between dx = 1 m and dx = 2 m. It is revealed that Tfb and a are higher in spring and summer. dx = 4 m is the optimum length of solar absorber. The amount of H2 produced from the biogas dry reforming reactor as well as the power generated by SOFC is the highest in August, resulting that it is prefer to produce H2 and to generate SOFC in summer.

The Joule–Thomson effect of (CO_(2)+H_(2)) binary system relevant to gas switching reforming with carbon capture and storage(CCS)

The Joule-Thomson effect is one of the important thermodynamic properties in the system relevant to gas switching reforming with carbon capture and storage(CCS). In this work, a set of apparatus was set up to determine the Joule-Thomson effect of binary mixtures(CO_(2)+ H_(2)). The accuracy of the apparatus was verified by comparing with the experimental data of carbon dioxide. The Joule-Thomson coefficients(μ_(JT)) for(CO_(2)+ H_(2)) binary mixtures with mole fractions of carbon dioxide(x_(CO_(2))= 0.1, 0.26, 0.5,0.86, 0.94) along six isotherms at various pressures were measured. Five equations of state EOSs(PR,SRK, PR, BWR and GERG-2008 equation) were used to calculate the μ_(JT)for both pure systems and binary systems, among which the GERG-2008 predicted best with a wide range of pressure and temperature.Moreover, the Joule-Thomson inversion curves(JTIC) were calculated with five equations of state. A comparison was made between experimental data and predicted data for the inversion curve of CO_(2). The investigated EOSs show a similar prediction of the low-temperature branch of the JTIC for both pure and binary systems, except for the BWRS equation of state. Among all the equations, SRK has the most similar result to GERG-2008 for predicting JTIC.

A Preliminary Study on the Rural Land System Reform in the Context of Rural Revitalization

With the deepening of reform and opening up,the rural land system has experienced the evolution from contracting to transfer to the current rural revitalization strategy,and has always been closely linked to the well-being of farmers and the vigorous development of the rural economy.The reform of this system is not only a key driving force for rural economic development,but also an important cornerstone for realizing the rural revitalization strategy.Through in-depth analysis of the connotation of rural revitalization and rural land system reform,this study discusses in detail the internal dynamic mechanism of rural land system reform driving rural revitalization,and comprehensively analyzes the current implementation of rural land system reform.On this basis,this study puts forward the strategic concept of promoting the rural land system reform in the context of rural revitalization.Studies have shown that the rural land system reform has mainly played a positive role in the following four aspects in promoting rural revitalization:providing a solid material foundation for rural revitalization,optimizing the allocation of rural resources,promoting the transformation and upgrading of rural industrial structure,and promoting rural social harmony and stability.In the context of the current rural revitalization,the rural land system reform is undoubtedly one of the core issues of China s rural development.In order to further improve this system,we need to continue to optimize and innovate the rural land transfer system,the homestead reform system,and the rural collective construction land market entry system.

Practical Research on Promoting the Reform of“One Field for One Household”in Guoyang County

In recent years,the problem of farmland fragmentation has become a major obstacle to the development of modern agriculture,and the reform of“one field for one household”can effectively sort out cultivated land resources,increase contracted land area,improve land utilization rate,and effectively solve the problems of contracted land dispersion and farmland fragmentation in rural areas.This paper systematically anatomized the practice and effects of“one household,one field”reform in Guoyang County,analyzed the problems existing in the implementation process,and put forward corresponding suggestions and countermeasures,in order to provide experience and reference for the reform of one field in other regions.

From Cooperation to Confrontation:The Collapse of the Reform Concept Led by Austria-Hungary and Russia in Macedonia(1903-1908)

As two major Great Powers in the geopolitics of the Balkans,the relationship between Austria-Hungary and Russia directly affected the stability of the political situation in Europe and the Balkans.At the beginning of the 20th century,the Austro-Russian cooperation dominated the Macedonian reforms,but with the deepening of the reforms,the structural contradictions between the two countries were fully exposed,and the original cooperative relationship went to a rupture.This drastically changed relationship became an important factor in the restructuring of relations between the Great Powers and the Balkan states before the First World War.