Confined Ni-In intermetallic alloy nanocatalyst with excellent coking resistance for methane dry reforming

Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two major greenhouse gases into value-added syngas or hydrogen.The main problem retarding its industrialization is the seriously coking formation upon the nickel-based catalysts.Herein,a series of confined indium-nickel(In-Ni)intermetallic alloy nanocatalysts(In_(x)Ni@SiO_(2))have been prepared and displayed superior coking resistance for DRM reaction.The sample containing 0.5 wt.%of In loading(In_(0.5)Ni@SiO_(2))shows the best balance of carbon deposition resistance and DRM reactivity even after 430 h long term stability test.The boosted carbon resistance can be ascribed to the confinement of core–shell structure and to the transfer of electrons from Indium to Nickel in In-Ni intermetallic alloys due to the smaller electronegativity of In.Both the silica shell and the increase of electron cloud density on metallic Ni can weaken the ability of Ni to activate C–H bond and decrease the deep cracking process of methane.The reaction over the confined InNi intermetallic alloy nanocatalyst was conformed to the Langmuir-Hinshelwood(L-H)mechanism revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS).This work provides a guidance to design high performance coking resistance catalysts for methane dry reforming to efficiently utilize these two main greenhouse gases.

Trifunctional strategy for the design and synthesis of a Ni-CeO_(2)@SiO_(2)catalyst with remarkable low-temperature sintering and coking resistance for methane dry reforming

In this study,a trifunctional strategy was developed to prepare a confined Ni-based catalyst(Ni-CeO_(2)@SiO_(2))for dry reforming of methane(DRM)of two main greenhouse gases-CO_(2)and CH_(4).The Ni-CeO_(2)@SiO_(2)catalyst was fabricated by utilizing the confinement effect of the SiO_(2)shell and the synergistic interaction between Ni-Ce and the decoking effect of CeO_(2).The catalysts were systematically characterized via X-ray diffraction,N_(2 )adsorption/desorption,transmission electron microscopy,energy dispersive X-ray spectroscopy,hydrogen temperature reduction and desorption set by program,oxygen temperature program desorption,Raman spectroscopy,thermogravimetric analysis,and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements to reveal their physicochemical properties and reaction mechanism.The Ni-CeO_(2)@SiO_(2)catalyst exhibited higher activity and stability than the catalyst synthesized via the traditional impregnation method.In addition,no carbon deposition was detected over Ni-CeO_(2)@SiO_(2)after a 100 h durability test at 800℃,and the average particle size of Ni nanoparticles(NPs)in the catalyst increased from 5.01 to 5.77 nm.Remarkably,Ni-CeO_(2)@SiO_(2)also exhibited superior low-temperature stability;no coke deposition was observed when the catalyst was reacted at 600℃ for 20 h.The high coking and sintering resistance of this confined Ni-based DRM catalyst can be attributed to its trifunctional effect.The trifunctional strategy developed in this study could be used as a guideline to design other high-performance catalysts for CO_(2)and CH4 dry forming and accelerate their industrialization.

Unravelling the Anomalous Coking Resistance over Boron Nitride-Supported Ni Catalysts for Dry Reforming of Methane

Metal oxides have been used as the supports for heterogeneous catalysis formany years,but they still suffer from coking in some high-temperature applications.The main reasons for coking are the uncontrollable dissociation of C-H and the overbalance between carbon deposition and removal.Herein,we find a boron nitride(BN)-immobilized Ni catalyst shows unprecedented coking resistance in dry reforming of methane via the incomplete decomposition of methane.Unlike the Ni-based catalysts supported by traditional metal oxides,BN-supported Ni accelerates the first C-H dissociation while inhibiting the breaking of the final C-H bond;hence,the suppression of the complete decomposition of methane thoroughly addresses the coking issue.This work reveals the fundamental reason for the coking resistance over BN-supported Ni catalysts is selective activation of the C-H bond,which can provide an inspiring idea for other applications.

Coking-resistant Ni-ZrO_2/Al_2O_3 catalyst for CO methanation

Highly coke-resisting ZrO2-decorated Ni/A1203 catalysts for CO methanation were prepared by a two-step process. The support was first loaded with NiO by impregnating method and then modified with ZrO2 by deposition-precipitation method （IM-DP）. Nitrogen adsorption- desorption, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetdc analysis, H2 temperature- programmed reduction and desorption, NH3 temperature-programmed desorption, and zeta potential analysis were employed to characterize the samples. The results revealed that, compared with the catalysts with the same composition prepared by co-impregnation （CI） and sequential impregnation （SI） methods, the Ni/A1203 catalyst prepared by IM-DP showed much enhanced catalytic performance for syngas methanation under the condition of atmospheric pressure and a high weight hourly space velocity of 120000 mL.g-1 .h-1. In a 80 h life time test under the condition of 300-600 ~C and 3.0 MPa, this catalyst showed high stability and resistance to coking, and the amount of deposited carbon was only 0.4 wt%. On the contrary, the deposited carbon over the catalyst without ZrO2 reached 1.5 wt% after a 60 h life time test. The improved catalytic performance was attributed to the selective deposition of ZrO2 nanoparticles on the surface of NiO rather than A1203, which could he well controlled via changing the electrostatic interaction in the DP procedure. This unique structure could enhance the dissociation of CO2 and generate surface oxygen intermediates, thus preventing carbon deposition on the Ni particles in syngas methanation.

Effect of silicon carbide-based iron catalyst on reactor optimization for non-oxidative direct conversion of methane

The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.

High-performance phosphate supported on HZSM-5 catalyst for dehydration of glycerol to acrolein

The purpose of this study is to increase acrolein yield and capability of coking resistance in the reaction of glycerol dehydration to acrolein by assembling metal phosphate supported on HZSM-5 catalyst. The as-prepared catalysts were characterized by XRD, SEM, EDS, BET, NH_3-TPD, CO_2-TPD and Py-IR techniques. It was found that metal phosphate species were incorporated into the porous structure of HZSM-5 zeolites, thus influencing the surface and textural physico-chemical properties of the supporters. The alkaline-treated HZSM-5 catalyst promoted the dispersion of phosphate species on the carriers. Moreover, the amount of strong acidity was tremendously improved by adding the different metal hydrophosphates and the catalysts show high catalytic activity. In this present work, the Sn1/4 H_2PO_4/HZSM-5 catalyst exhibited good performance in the catalytic activity and coking resistant ability, which resulted in a high acrolein yield of 83% initially and acrolein yield of 68% after 30 h. The acidity, especially the ratio of strong to weak acid, plays an important role in promoting acrolein yield and stability simultaneously.

Morphology effect of zirconia support on the catalytic performance of supported Ni catalysts for dry reforming of methane

An immature pinecone shaped hierarchically structured zirconia （ZrO2-ipch） and a cobblestone-like zirconia nanoparticulate （ZrO2-cs）, both with the monoclinic phase （m-phase）, were synthesized by the facile hydrothermal method and used as the support for a Ni catalyst for the dry reforming of methane （DRM） with CO2. ZrO2-ipch is a much better support than ZrO2-cs and the traditional ZrO2 irregular particles made by a simple precipitation method （ZrO2-ip）. The supported Ni catalyst on ZrO2-ipch （Ni/ZrO2-ipch） exhibited outstanding catalytic activity and coke-resistant stability compared to the ones on ZrO2-cs （Ni/ZrO2-cs） and ZrO2-ip （Ni/ZrO2-ip）. Ni/ZrO2-ip exhibited the worst catalytic performance. The origin of the significantly enhanced catalytic performance was revealed by characterization including XRD, N2 adsorption measurement （BET）, TEM, H2-TPR, CO chemisorption, CO2-TPD, XPS and TGA. The superior catalytic activity of Ni/ZrO2-ipch to Ni/ZrO2-cs or Ni/ZrO2-ip was ascribed to a higher Ni dispersion, increased reducibility, enhanced oxygen mo- bility, and more basic sites with a higher strength, which were due to the unique hierarchically structural morphology of the ZrO2-ipch support. Ni/ZrO2-ipch exhibited better stability for the DRM reaction than Ni/ZrO2-ip, which was ascribed to its higher resistance to Ni sintering due to a strengthened metal-support interaction and the confinement effect of the mesopores and coke deposition resistance. The higher coking resistance of Ni/ZrO2-ipch for the DRM reaction in comparison with Ni/ZrOz-ip orignated from the coke-removalabitity of the higher amount of lattice oxygen and more basic sites, confirmed by XPS and CO2-TPD analysis, and the stabilized Ni on the Ni/ZrO2-ipch catalyst by the confinement effect of the mesopores of the hierarchical ZrO2-ipch sup- port. The superior catalytic performance and coking resistance of the Ni/ZrO2-ipch catalyst makes it a promising candidate for synthesis gas production from the DRM reaction.

Methane dry reforming on Ni/La_2Zr_2O_7 treated by plasma in different atmospheres

A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry reforming of methane（DRM）. It is found that all of the plasma treated catalysts show evidently improved activity and coke resistance in comparison with the non-plasma treated one. The best performance is achieved on Ni/La2Zr2O7–H2P–C,a catalyst treated in H2 plasma before calcination. TGA-DSC and SEM demonstrate that carbon deposition is significantly suppressed on all of the plasma treated samples. Moreover,XRD and TEM results testify that both Ni O and Ni sizes on the calcined and reduced samples treated by plasma are also decreased,which results in higher Ni metal dispersion on the reduced and used catalysts and enhances the interactions between Ni sites and the support. It is believed that these are the inherent reasons accounting for the promotional effects of plasma treatment on the reaction performance of the Ni/La2Zr2O7 pyrochlore catalysts.

Coke-Resistant Ni-based Catayst for Partial Oxidation and CO_2-Reforming of Methane to Syngas

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Dry reforming of methane on active and coke resistant Ni/Y_2Zr_2O_7 catalysts treated by dielectric barrier discharge plasma

In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.

Coke-resistant Au–Ni/MgAl2O4 catalyst for direct methanation of syngas

Carbon deposition is one of the major issues for catalytic methanation,especially when using high CO content syngas(such as H2/CO=1)due to the inevitable Boudouard reaction.Here we report the significant enhancement on the coke-resistance of Ni/MgAl2 O4 catalyst during methanation by modifying with Au.The coke-resistant property was increased with Au addition while the catalytic activity decreased with excess Au.High and stable syngas conversions can be obtained over Au-Ni/MgAl2O4 catalyst at 450-500℃.With comprehensive characterizations by using BET,H2 chemisorption,H2-TPR,XPS,XRD,STEM,EDS,TEM,TG/DTA,Raman and TPH,we found that Au and Ni formed bimetallic nanoparticles of^10 nm with electron donation from Ni to Au.The deposited carbon on the spent Au-Ni/MgAl2O4 is very similar to that on the spent Ni/MgAl2O4 in the nature and in the gasification behaviour but is significantly less.These results suggest that the enhanced coke-resistance of Au-Ni/MgAl2 O4 is presumably due to the suppression on CO disproportionation by modifying Ni with Au.

Hierarchical Porous ZSM-5 Zeolite Synthesized by in situ Zeolitization and Its Coke Deposition Resistance in Aromatization Reaction

Hierarchical ZSM-5 zeolites with micro-, meso- and macroporosity were prepared from diatomite zeolitization through a vapor-phase transport process on solid surfaces. The aromatization performance of the catalysts was in- vestigated on a fixed bed reactor by using FCC gasoline as feedstock. The crystal phase, morphology, pore struc- tures, acidity and coke depositions of the hierarchical ZSM-5 zeolites were characterized by means of X-ray diffrac- tion （XRD）, scanning electron microscope （SEM）, N2 adsorption/desorption, Fourier transform infrared （FT-IR） and thermogravimetry-mass spectrogram （TG-MS）, respectively. The results show that the prepared hierarchical ZSM-5 zeolite possesses excellent porosity and high crystallinity, displaying an improved aromatization performance and carbon deposition resistance due to its meso- and macroporous structures.

Improving Catalytic Stability and Coke Resistance of Ni/Al_(2)O_(3) Catalysts with Ce Promoter for Relatively Low Temperature Dry Reforming of Methane Reaction

A series of Ni catalysts supported on alumina with different Ce contents(1.0%–6.0%,mass fraction)was prepared by the impregnation method and used for dry reforming of methane(DRM)at a relatively low temperature of 650°C.The promotion effect of Ce with different loading amounts on the physicochemical properties of the catalysts was systematically characterized by transmission electron microscopy(TEM),X-ray diffraction(XRD),N_(2) adsorption-desorption,thermo elemental IRIS Intrepid inductively coupled plasma atomic emission spectrometer(ICP-AES),UV-visible diffuse reflectance spectroscopy(UV-Vis DRS),Fourier transformation infrared(FTIR)spectra,H_(2)-temperature programmed reduction(H_(2)-TPR)analysis,H_(2)-temperature programmed desorption(H_(2)-TPD),and The X-ray photoelectron spectroscopy(XPS)techniques.The results indicate that all the catalysts mainly exist in the NiAl_(2)O_(4) phase after being calcined at 750°C with small Ni particle sizes due to the strong metal-support interaction derived from the reduction of the NiAl_(2)O_(4) phase.The Ce-promoted catalysts show better catalytic performance as well as the resistance against sintering of Ni particles and deposition of carbon compared to the Ni/Al_(2)O_(3) catalyst.The Ni-6Ce/Al_(2)O_(3) exhibits the best catalytic stability and coke resistance among the four catalysts studied,which is due to its small Ni nanoparticles sizes,excellent reducibility as well as high amount of active oxygen species.In a 400 h stability test for DRM reaction at 650°C,Ni-6Ce/Al_(2)O_(3) exhibits less coke deposition and small growth of Ni nanoparticles.This work provides a simple way to preparing the Ni-Ce/Al_(2)O_(3) catalyst with enhanced catalytic performance in DRM.The Ni-6Ce/Al_(2)O_(3) catalyst has great potential for industrial application due to its anti-sintering ability and resistance to carbon deposition.

Effect of Coke Reaction Index on Reduction and Permeability of Ore Layer in Blast Furnace Lumpy Zone Under Non-Isothermal Condition

Reasonable control on CRI（coke reaction index）is one of the key factors for BF（blast furnace）low-carbon smelting.However,there are contrary opinions.One is increasing CRI to improve reaction efficiency in BF and the other is decreasing CRI to suppress coke degradation in furnace.Different methods are adopted to realize effective catalysis（increasing CRI）and passivation（decreasing CRI）of coke.Simulation tests of coke in BF lumpy zone under gradual temperature rising have been done.Effect of CRI on gas composition,ore reduction,burden column permeability and heat reserve zone′s temperature under non-isothermal condition are studied.Then combined with iron making calculations,a novel BF operation suggestion is proposed as coke nut with small size be catalyzed and mixed with ore while skeletal coke with large size be passivated and separately charged into BF.