Ni-based catalysts doped with copper additives were studied on their role in ethanol steam reforming reaction.The effects of Ca content,support species involving Al2O3-SiO2,Al2O3-MgO,Al2O3-ZnO,and Al2O3-La2O3,on the catalytic performance were studied.Characterizations by TPR,XRD,NH3-TPD,XPS,and TGA indicated that catalysts 30Ni5Cu/Al2O3-MgO and 30NiSCu/Al2O3-ZnO have much higher H2 selectivity than 30NiSCu/Al2O3-SiO2,as well as good coke resistance.H2 selectivity for 30Ni5Cu/Al2O3-MgO catalyst was 73.3% at 450℃ and increased to 94.0% at 600 ℃,whereas for 30NiSCu/Al2O3-ZnO catalyst,the H2 selectivity was 63.6% at 450 ℃ and 95.2% at 600 ℃.These Al2O3-MgO and Al2O3-ZnO supported Ni-Cu bimetallic catalysts may have important applications in the production of hydrogen by ethanol steam reforming reactions....
La2O2CO3 was prepared by calcination of La2 (CO3)3 in the air.Catalysts Ni-Fe/La2O2CO3 with different mole ratios of Ni to Fe,Ni/La2O2CO3 and Fe/La2O2CO3 were prepared by impregnation method.The catalytic properties were evaluated on steam reforming of ethanol (SRE) from 300 to 700 ℃ under atmospheric pressure and the samples were characterized by Brunauer-Emmett-Teller method (BET),X-ray diffraction (XRD) and temperature programmed reduction (TPR).The results showed that Ni-Fe bimetallic catalysts exhibited higher activities than single metallic catalysts,which was attributed to the co-existence of well dispersed Ni,Fe and LaFeyNi1 yO3.It was found that the catalyst Ni-Fe/La2O2CO3 containing 10 wt.% Ni and 3 wt.%-5 wt.% Fe showed the best performance,the conversion of ethanol was 100%,the selectivity of H2 was higher than 90%,and the selectivity of CO was lower than 1.5% at 400 ℃....
NiO-Ce0.5Zr0.5O2catalysts were prepared by citrate method and used for hydrogen production from steam reforming of ethanol (SRE). The effect of nickel content and space velocity on the catalytic performance was investigated. The prepared catalysts were character-ized with XRD and thermal analysis techniques. 20%NiO-Ce0.5Zr0.5O2 catalyst was very active and selective for hydrogen production via SRE, in which ethanol conversion of 100% could be obtained with feed component of 20% (H2O+EtOH) and 80% N2, water/ethanol of 3/1 in molar ratio at 350 ℃. Also, the catalyst showed good stability for anti-sintering and carbon-resistance. The XRD illuminated that both NiO and Ce0.5Zr0.5O2 crystal sizes were very small in NiO-Ce0.5Zr0.5O2 catalyst, and Ce0.5Zr0.5O2 solid solution was formed....
Dielectric barrier discharge(DBD)was used for the generation of hydrogen from ethanol reforming.Effects of reaction conditions,such as vaporization temperature,ethanol flow rate,water/ethanol ratio,and addition of oxygen,on the ethanol conversion and hydrogen yield,were studied.The results showed that the increase of ethanol flow rate decreased ethanol conversion and hydrogen yield,and high water/ethanol ratio and addition of oxygen were advantageous.Ethanol conversion and hydrogen yield increased with the vaporization room temperature up to the maximum at first,and then decreased slightly.The maximum hydrogen yield of 31.8% was obtained at an ethanol conversion of 88.4% under the optimum operation conditions of vaporization room temperature of 120℃,ethanol flux of 0.18 mL/min,water/ethanol ratio of 7.7 and oxygen volume concentration of 13.3%....
通过建立包含动量、质量传递以及化学反应动力学方程的多物理场耦合数值模型,对以Ni为催化剂的甲烷二氧化碳重整制合成气过程中的积炭效应展开了计算。计算结果阐明了包含多孔介质催化剂段的反应通道中的速度场及压力分布,以及在通道中随气体流动以及沉积在催化剂表面的碳颗粒的浓度分布,分析了积炭对催化剂孔隙率和渗透率的影响,并进一步讨论了甲烷浓度以及温度对积炭产生的影响,最后提出了消减积炭的方法。本文的结论对于进一步研究 Ni 基催化剂在 CH4-CO2重整制合成气反应中积炭效应的消减有一定的指导意义。...
A thermodynamic analysis of methane oxidative reforming was carried out by Gibbs energy minimization (at constant pressure and temperature) and entropy maximization (at constant pressure and enthalpy) methods,to determine the equilibrium compositions and equilibrium temperatures,respectively.Both cases were treated as optimization problems (non-linear programming formulation).The GAMS(R) 23.1 software and the CONOPT2 solver were used in the resolution of the proposed problems.The hydrogen and syngas production were favored at high temperatures and low pressures,and thus the oxygen to methane molar ratio (O2/CH4) was the dominant factor to control the composition of the product formed.For O2/CH4 molar ratios higher than 0.5,the oxidative reforming of methane presented autothermal behavior in the case of either utilizing O2 or air as oxidant agent,but oxidation reaction with air possessed the advantage of avoiding peak temperatures in the system,due to change in the heat capacity of the system caused by the addition of nitrogen.The calculated results were compared with previously published experimental and simulated data with a good agreement between them....
The effects of factors such as the molar ratio of H2O to CH4 (n(H2O)/n(CH4)), methane conversion temperature and time on methane conversion rate were investigated to build kinetic model for reforming of coke-oven gas with steam. The results of experiments show that the optimal conditions for methane conversion are that the molar ratio of H2O to CH4 varies from 1.1 to 1.3and the conversion temperature varies from 1 223 to 1 273 K. The methane conversion rate is more than 95% when the molar ratio ofH2O to CH4 is 1.2, the conversion temperature is above 1 223 K and the conversion time is longer than 0.75 s. Kinetic model of methane conversion was proposed. All results demonstrate that the calculated values by the kinetic model accord with the experimental data well, and the error is less than 1.5%....
Auto-thermal reforming of methane, combining partial oxidation and reforming of methane with CO2 or steam, was carried out with Pt/Al2O3, Pt/ZrO2 and Pt/CeO2 catalysts, in a temperature range of 300-900 ℃. The auto-thermal reforming occurs in two simultaneous stages, namely, total combustion of methane and reforming of the unconverted methane with steam and CO2, with the O2 conversion of 100% starting from 450 ℃. For combination with CO2 reforming, the Pt/CeO2 catalyst showed the lowest initial activity at 800 ℃, and the highest stability over 40 h on-stream. This catalyst also presented the best performance for the reaction with steam at 800 ℃. The higher resistance to coke formation of the catalyst supported on ceria is due to the metal-support interactions and the higher mobility of oxygen in the oxide lattice....
In the current study simultaneous reactions of hydrodesulfurization (HDS) of dibenzothiophene (DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic ( Co-Mo/Al2O3 and Ni-Mo/Al2O3 ) and tri-metallic ( Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3 ) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3> Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism....
A novel design of plate-type microchannel reactor has been developed for fuel cell-grade hydrogen production.Commercial Cu/Zn/Al2O3 was used as catalyst for the reforming reaction,and its effectiveness was evaluated on the mole fraction of products,methanol conversion,hydrogen yield and the amount of carbon monoxide under various operating conditions.Subsequently,0.5 wt% Ru/Al2O3 as methanation catalyst was prepared by impregnation method and coupled with MSR step to evaluate the capability of methanol processor for CO reduction.Based on the experimental results,the optimum conditions were obtained as feed flow rate of 5 mL/h and temperature of 250℃,leading to a low CO selectivity and high H2 yield.The designed reformer with catalyst coated layer was compared with the conventional packed bed reformer at the same operating conditions.The constructed fuel processor had a good performance and excellent capability for on-board hydrogen production....
The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming (DR) and methanol decomposition (DE) were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test....
The catalytic performances of methanol steam reforming reactions on CuZn(Zr)AlO catalysts were studied. When the ZrO2 promoter was added to a CuZnAlO catalyst, its methanol conversion,H2 production and H2 selectivity improved greatly. By using the #COPZr-2 catalyst as an example,which exhibited the best catalytic performance, the optimized reaction conditions were established to be:250 ℃, 0.1 MPa, H2O/MeOH=1.3, WHSV=3.56 h-1, and without carrier gas. A 150 h stability test of the #COPZr-2 catalyst showed that the catalyst had good stability, as the methanol conversion and H2 production could be kept at 88% and 83% respectively. Moreover, outlet H2 and CO contents were >63%and 0.20%-0.31%, respectively....
Cu/ZnAlO catalysts derived from hydroxycarbonate precursors containing hydrotalcite-likelayered double hydroxides (LDHs) were studied. The influence on the performance of the catalysts wasalso studied when the Al in the Cu/ZnAlO catalyst was partly or completely replaced by Zr or Ce....
Nickel catalysts are effective for the steam reforming of tar derived from biomass pyrolysis,but the improvement is needed in terms of activity,stability,suppression of coke deposition and aggregation,and regeneration.Our recent development of Ni-based catalysts for the steam reforming of tar is reviewed including the modification with CeO2 (or MnO),trace Pt,and MgO.The role of additives such as CeO2,MnO,Pt,and MgO is also discussed....