碳化镍钼催化剂的制备及其甲烷干气重整活性(英文)

Nickel molybdenum carbide catalysts were prepared and their activities in the CO2 reforming of methane at a low CO2/CH4 reactant ratio were investigated using a microreactor at atmospheric pressure and at 973 K.The effect of the catalyst preparation method and the Ni/Mo ratio on the increase in catalyst life and the promotion of catalytic activity were investigated using N2 adsorption,X-ray diffraction, temperature-programmed carburization,temperature-programmed reaction,and a reforming reaction.The 25Ni75Mo catalyst that was carburized at 813 K exhibited the highest hydrogen formation ability and gave the least carbon deposition.The incomplete carburization of the Mo oxide species in the catalyst that was carburized at a lower temperature gradually gave a more active carburized species.The NiMoOxCy in the catalyst was more active in hydrogen formation during the dry reforming of methane whileβ-Mo2C andη-Mo3C2 were less active.     

Thermodynamic analysis of mixed and dry reforming of methane for solar thermal applications

Thermodynamic analysis of the reforming of methane with carbon dioxide alone ("dry reforming") and with carbon dioxide and steam together ("mixed reforming") is performed as part of a project which investigates the suitability of these endothermic reactions for the storage of solar thermal energy. The Gibbs free energy minimization method was employed to identify thermodynamically optimal operating conditions for dry reforming as well as mixed reforming with a desired H2/CO molar ratio of 2. The non-stoichiometric equilibrium model was developed using FactSage software to conduct the thermodynamic calculations for carbon formation, H2/CO ratio, CH4 conversion and H2 yield as a function of reaction temperature, pressure and reactant molar ratios. Thermodynamic calculations demonstrate that in the mixed reforming process, optimal operating conditions in a carbon-free zone are under H2O/CH4 /CO2 =1.0/1.0/0.5, p = 1 to 10 bar and T = 800 to 850℃ for the production of syngas with a H2 /CO molar ratio of 2. Under the optimal conditions, the maximum H2 yield of 88.0% is achieved at 1 bar and 850℃ with a maximum CH4 conversion of 99.3%. In the dry reforming process, a carbon formation regime is always present at a CO2/CH4 molar ratio of 1 for T = 700 1000℃ and p = 1-30 bar, whereas a carbon-free regime can be obtained at a CO2/CH4 molar ratio greater than 1.5 and T≥800℃.     

Reaction parameters influence on the catalytic performance of copper-silica aerogel in the methanol steam reforming

Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO selectivity were investigated.M ethanol conversion was increased considerably in the range of about 240-300,after which it increased at a slightly lower rate.The used feed flowrate,steam to methanol molar ratio and carrier gas flowwere 1.2-9.0 m L/h,1.2-5.0 and 20-80 m L/min,respectively.Reducing the feed flowrate increased the H_2 production rate.It was found that an increase in the water to methanol ratio and decreasing the carrier gas flowrate slightly increases the H2production rate.Increasing the water to methanol ratio causes the lowest temperature in which CO formation was observed to rise,so that for the ratio of 5.0 no CO formation was detected in temperatures lower than 375℃.In all conditions,by approaching the complete conversion,increasing the main product concentration,increasing the temperature and contact time,and decreasing the steam to methanol ratio,the CO selectivity was increased.These results suggested that CO was formed as a secondary product through reverse water-gas shift reaction and did not participate in the methanol steam reforming reaction mechanism.     

Effects of Ce/Zr ratio on the structure and performances of Co-Ce_（1-x）Zr_xO_2 catalysts for carbon dioxide reforming of methane

The Co-incorporated Ce1-xZrxO2 catalysts were prepared by co-precipitation for carbon dioxide reforming of methane. The ratio of Ce to Zr was varied to optimize the performances of co-precipitated Co-Ce-Zr-Ox catalysts. The prepared catalysts were characterized by various physico-chemical characterization techniques including TPR, X-ray diffraction, N2 adsorption at low temperature, XPS and CO2-TPSR. The co-precipitated Co-Ce0.8Zr0.2O2 sample containing 16% CoO exhibited a higher catalytic activity among the five catalysts, and the activity was maintained without significant loss during the reaction for 60 h. Under the conditions of 750 ℃, 0.1 MPa, 36000 ml/(h·g{cat}), and CO2/CH4 molar ratio of 1 : 1, the CO2 conversion over this catalyst was 75% while the CH4 conversion was 67%. The cubic Ce0.8Zr0.2O2 facilitated a higher dispersion and a higher reducibility of the cobalt component, and the apparent activation energy for Co-Ce0.8Zr0.2O2 sample was 49.1 kJ/mol in the CO2/CH4 reforming reaction. As a result, the Co-Ce0.8Zr0.2O2 sample exhibited a higher activity and stability for the reforming of CH4 with CO2.     

Kinetics of methanol steam reforming over COPZr-2 catalyst

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.     

STUDIES ON FISCHER TROPSCH SYNTHESIS OVER Fe-Cu-K CATALYST Ⅰ.CATALYTIC PERFORMANCE

The influence of reaction pressure, temperature, space velocity (GHSV), particle size of catalyst and H2/CO ratio of feed-gas on the steady-state product distribution, conversion of CO, H2 and syngas, olefin to paraffin ratio and CO2/ H2O ratio for FTS reaction were investigated using a coprecipitated copper- potassium promoted iron catalyst. The test was carried out in a fixed-bed reactor. Increasing the reaction temperature from 493. 2 to 5-13. 2 K shifted the hydrocarbon distribution toward the heavier hydrocarbons (C5-C23) and selectively increased CO conversion to CO2. The hydrocarbon distribution was found to be dependent on the H2/CO feed-gas ratio in the range from 1.23 to 2. 22. The CO2/H2O ratio in product decreased as the flow of feed-gas rate increased, which suggests that H2O is a primary product and its reaction with CO to form CO2 occurs via a secondary process. The CO conversion increased with the decrease of catalyst particle size from 10 to 60 mesh (2. 0- 0. 3 mm), while the CO convers     

Kinetics of Carbon Deposition on Hexaaluminate LaNiAl11O19 Catalyst During CO2 Reforming of Methane

In this paper, the properties of carbon deposited on hexaaluminate LaNiAl11O19 catalyst were characterized by X-ray photoelectron spectroscopy (XPS), and in the meantime, the amount of carbon deposited on the catalyst, after both CH4 decomposition and CO2 reforming of CH4, was determined by means of thermogravimetric analysis (TGA), respectively. The rates of carbon deposited on the catalyst were also investigated and the apparent kinetic equation of CO2 reforming of CH4: vc = kp0.72(CH4).p-0.55(CO2), was established by analyzing the relation between the rates of deposited carbon and the pressure ratio of CH4 and CO2.     

Investigation on the active phase of CoMo catalyst for selective HDS by low temperature in situ FT-IR

The CoMo/Al₂O₃ catalysts with different metal loading were studied by low temperature in situ FT-IR using CO as probe molecule which appears to be a powerful method by giving rise to signals specific for unpromoted and promoted Mo sites.The result revealed that the increase of CoMoS phase on the catalyst surface improves the HDS activity and selectivity.The ratio of active site number of CoMoS and MoS₂ correlates linearly with HDS selectivity,which provides an effective tool for developing industrial selective HDS catalysts.     

Comparative study on the reaction of methane over a ZnO bed in the absence and presence of CO2

The reaction of zinc oxide with methane in the absence and presence of CO2 were theoretically and experimentally investigated using HSC Chemistry 5.1 software and a fixed bed reactor, respectively. In the absence of CO2 at 1193 K, the reduction of ZnO was accompanied with methane cracking, and metallic zinc, CO, and H2 were the main reaction products. This system could be utilized for the co-production of metallic zinc and synthesis gas, in which ZnO was a donor of oxygen. In the presence of CO2, ZnO plays as a catalyst in the CO2 reforming of methane and produces syngas with the average H2/CO ratio of 0.88 at 1193 K, which was close to the total reaction theoretic value of 1. It was also found that higher temperature favored high CH4 and CO2 conversions. XRD technique was used to characterize the ZnO species. The result showed that there were no differences in the peak profiles of the XRD patterns of the ZnO powder obtained before and after passing the CH4/CO2 mixed gases for 6 h at 1193 K. It is suggested that ZnO functions as a catalyst according to the redox cycle and metallic zinc plays the role of intermediate product in this process.     

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al_2O_3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ～ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated.Catalysts of xwt%Ni/α-Al2O3(x=2.5,5,8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate.XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst,as compared with the other prepared catalyst samples.An increase of the Ni loading to more than 5wt% led to a reduction in the Ni dispersion.In addition,by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction,the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.     

Intrinsic kinetics of oxidative dehydrogenation of propane in the presence of CO2 over Cr/MSU-1 catalyst

The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinetic data were obtained under the following conditions: 490-530 °C, space velocity of 3600?6000 mL·h-1·g-1 and 3/1 molar ratio for CO2/C3H8 under normal pressure. Based on Langmuir-Hinshelwood mechanism, the kinetic models were established, and they were validated by statistical analysis. The parameters were estimated using Simplex Method combined with Universal Global Optimization Algorithm. The model, taking the surface reaction process as the rate-determining step, is the best one in agreement with the experimental data.     

Effect of MgO promoter on Ni-based SBA-15 catalysts for combined steam and carbon dioxide reforming of methane

A series of Ni/SBA-15 catalysts with Ni contents ranging from 5 wt% to 15 wt%, as well as another series of 10%Ni/MgO/SBA-15 catalysts, in which the range of the MgO content was from 1 wt% to 7 wt%, were prepared, and their catalytic performances for the reaction of combined steam and carbon dioxide reforming of methane were investigated in a continuous flow microreactor. The structures of the catalysts were characterized using the XRD, H2-TPR and CO2-TPD techniques. The results indicated that the CO selectivity for this reaction was very close to 100%, and the H2/CO ratio of the product gas could be controlled by changing the H2O/CO2 molar ratio of the feed gas. The simultaneous and plentiful existing of steam and CO2 had a significant influence on the catalytic performance of the 10%Ni/SBA-15 catalyst without modification. After reacting at 850 °C for 120 h over this catalyst, the CH4 conversion dropped from 98% to 85%, and the CO2 conversion decreased from 86% to 53%. However, the 10%Ni/3%MgO/SBA-15 catalyst exhibited a much better catalytic performance, and after reacting for 620 h, the CO2 conversion over this catalyst dropped from 92% to around 77%, while the CH4 conversion was not decreased. Oxidation of the Ni0 species as well as carbon deposition during the reaction were the main reasons for the deactivation of the catalyst without modification. On the other hand, modification by the MgO promoter improved the dispersion of the Ni0 species, and enhanced the CO2 adsorption affinity which in turn depressed the occurring of carbon deposition, and thus retarded the deactivation process.     

用于甲烷水蒸气重整的镍基催化剂的失活和再生

The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),transmission electron microscopy(TEM),and carbon & sulfur analyzer. The Ni particle size was estimated from XRD patterns and TEM graphs. The agglomeration of nickel particle and the poison by sulfur components were recognized as the main reasons in deactivation of Arak and Razi catalysts,respectively. The activity of the used catalysts before and after regeneration was measured on methane steam reforming at a CH4:H2O ratio of 1:3 at 850 oC. The regeneration processes for Arak and Razi samples were performed with CO2 as an oxidative atmosphere and steam as a regenerating agent,respectively. The results show that,(1) no residual sulfur components were on the regenerated Razi catalyst surface without changing the structure of the catalyst and the regenerated catalyst has gained 80% of its catalytic activity,and that(2) the nickel particle size of regenerated Arak specimen decreased remarkably as measured by Debye-Scherrer equation from XRD patterns. TEM images were in agreement with the XRD results and indicated a decrease in nickel particle size of regenerated catalyst. Additionally,in both regenerated catalysts all the coke on the surface of the support was eliminated after regeneration.     

Effect of O2 and H2O on the tri-reforming of the simulated biogas to syngas over Ni-based SBA-15 catalysts

A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method. The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor. The stability of the catalyst was tested at 800 ℃. The results indicated that 10 wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas. Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6, GHSV = 24000 ml•g{cat}-1\cdoth-1 and the reaction temperatureT = 800 ℃, the conversions of CH4 and CO2 were 92.8% and 76.3%, respectively, and the yields of CO and H2 were 99.0% and 82.0%, respectively. The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.     

Nickel ferrite spinel as catalyst precursor in the dry reforming of methane:Synthesis,characterization and catalytic properties

Dry reforming of methane by CO2 using nickel ferrite as precursor of catalysts was investigated.Nickel ferrite crystalline particles were prepared by coprecipitation of nitrates with NaOH or ammonia followed by calcination,or by hydrothermal synthesis without calcination step.The textural and structural properties were determined by a number of analysis methods,including X-ray diffraction (XRD),Raman spectroscopy and X-ray photoelectron spectroscopy (XPS),among which X-ray diffraction (XRD) was at room and variable temperatures.All synthesized oxides showed the presence of micro or nanoparticles of NiFe2O4 inverse spinel,but Fe2O3 (hematite) was also present when ammonia was used for coprecipitation.The reducibility by hydrogen was studied by temperature-programmed reduction (TPR) and in situ XRD,which showed the influence of the preparation method.The surface area (BET),particle size (Rietveld refinement),as well as surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied according to the synthesis method.The catalytic reactivity was investigated using isopropanol decomposition to determine the acid/base properties.The catalytic performance of methane reforming with CO2 was measured with and without the pre-treatment of catalysts under H2 in 650-800 C range.The catalytic conversions of methane and CO2 were quite low but they increased when the catalysts were pre-reduced.A significant contribution of reverse water gas shift reaction accounted for the low values of H2 /CO ratio.No coking was observed as shown by the reoxidation step performed after the catalytic reactions.The possible formation of nickel-iron alloy observed during the study of reducibility by hydrogen was invoked to account for the catalytic behavior.     

Kinetics modeling for the mixed reforming of methane over Ni-CeO2/MgAl2O4 catalyst

Kinetics model was developed for the mixed (steam and dry) reforming of methane, which is useful for the control of H2/CO ratio. The equilibrium constants of reaction rate were determined using the experimental equilibrium data at different reaction temperatures, while the forward reaction rate constants were estimated using the experimental data under non-equilibrium (high inert fraction and high space velocity) conditions. The comparison between calculated and experimental data clearly showed that the developed model described satisfactorily, and further analysis using the parametric sensitivity determined the wall temperature and CO2 fraction in the feed gas as effective parameters for the manipulation of CH4 conversion and H2/CO ratio of synthesis gas under the equilibrium condition. Meanwhile, the inert fraction, rather than the residence time, was selected as additional parameter under non-equilibrium condition.     

Catalytic steam reforming of biomass over Ni-based catalysts: Conversion from poplar leaves to hydrogen-rich syngas

A series of Ni/SBA-15 catalysts with Ni contents from 5 wt%–20 wt%and CaO-12.5%Ni/SBA-15 catalysts with CaO contents from 1.4 wt%–9.8 wt%have been prepared.The structure of the catalysts was characterized using X-ray diffraction(XRD),N2 adsorption-desorption,transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS).The performance of catalytic steam reforming of the poplar leaves to the hydrogen-rich syngas was tested in a fixed-bed reactor.The results indicate that the 7.0wt%CaO-12.5wt%Ni/SBA-15 catalyst exhibits the best performance for the catalytic steam reforming of poplar leaves to hydrogen-rich syngas.The ratio of H2:CO can reach ca 5:1 in the hydrogen-rich syngas.The yield of H2 can reach 273.30 mL/g(poplar leaves).In the CaO-Ni/SBA-15 catalyst,Ni active component mainly fills the role of catalytic steam reforming of the poplar leaves,and CaO active component mainly plays the role as water-gas shift and CO2 sorbent.     

Novel smart supramolecular metallo-hydrogel that could selectively recognize and effectively remove Pb2+ in aqueous solution

A series of novel and simple ligands based on a biscarboxyl-functionalized benzimidazole derivative were synthesized.The experiments showed that the ligand L2 as a low molecular weight(LMW) hydrogelator could form stable metallo-hydrogels in the presence of up to 0.3 equiv.of lead ions.The metallo-hydrogels were characterized using powder X-ray diffraction,scanning electron microscopy(SEM),and Fourier transform infrared(FT-IR) spectroscopic techniques.When the molar ratio of L2:Pb2+ was in the range of 1:0.3 to 1:0.5 a translucent gel was produced.When the L2:Pb2+ molar ratio was higher than 1:0.5 the resulting gel tended to be opaque.The morphologies of these metallo-hydrogels were L2/Pb ratio dependent,ranging from worm-like to rod-shaped and nanofibrous.The FT-IR and X-ray diffraction(XRD) studies revealed that L2-Pb complexation was the main driving force for the formation of the metallo-hydrogels.In addition,these metallo-hydrogels exhibited outstanding thermostability and thermoreversibility,and displayed a reversible sol-gel transition induced by changes in pH and EDTA concentration.Importantly,ligand L2 showed an excellent capacity for the removal of Pb 2+ in aqueous solution through the formation of metallo-hydrogels.At a L2:Pb molar ratio of 1:0.5 and below,the concentration of residual Pb2+ was as low as 7.6×10-5 mol/L in aqueous solution,and the removal ratio was as high as 95.4%.These results demonstrate that multi-channel responsive smart metallo-hydrogels have the potential to be widely applied in materials science,and might provide the basis for lead pollution capture and removal.     

Ni/MgO catalyst prepared using atmospheric high-frequency discharge plasma for CO2 reforming of methane

A new type of Ni/MgO catalyst was prepared using atmospheric high-frequency discharge cold plasma. The influences of conventional method, plasma method, and plasma plus calcination method on the catalytic activity were studied and the CO2 reforming of methane was chosen as the probe reaction. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy, and CO2 temperature-programmed surface reaction techniques. The results suggested that the nickel-based catalyst prepared by plasma plus calcination method possessed a smaller particle size and a higher dispersion of active component, better low-temperature activity and enhanced anti-coking ability. The conversion of CO2 and CH4 was 90.70% and 89.37%, respectively, and the reaction lasted for 36 h without obvious deactivation under 101.325 kPa and 750°C with CO2/CH4 = 1/1.     

Rh doping effect on coking resistance of Ni/SBA-15 catalysts in dry reforming of methane

A series of SBA-15 supported bimetallic Rh–Ni catalysts with different weight ratio of Rh/Ni in the range of 0–0.04 were prepared for carbon dioxide reforming of methane. The doping effect of Rh on catalytic activity as well as carbon accumulation and removal over the catalysts was studied. The characterization results indicated that the addition of a small amount of Rh promoted the reducibility of Ni particles and decreased the Ni particle size. During the dry reforming reaction, the carbon deposition was originated from CH4 decomposition and CO disproportionation. The Rh–Ni catalyst with small metallic particle size inhibited the carbon formation and exhibited high efficiency in the removal of coke. In comparison with bare Ni-based catalyst, the Rh–Ni bimetallic catalysts showed high activity and stability in the dry reforming of methane.