Ni-Co/Mg-Al catalyst derived from hydrotalcite-like compound prepared by plasma for dry reforming of methane

Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.     

载体类型对Ni基催化剂甲烷干重整反应性能的影响

以不同载体负载NiO制备了甲烷干重整催化剂并对所制备的催化剂采用等温氮气吸附、XRD、H₂-TPR、H₂化学吸附等进行了表征。结果表明,载体性质对NiO的存在状态影响较大。SiO₂、TiO₂以及ZrO₂与NiO的相互作用较弱,催化剂易于被还原活化,而正是由于其与NiO的弱相互作用,导致活性金属在反应过程中易迁移聚集而失活。Al₂O₃和MgO均与NiO有强相互作用,易分别生成NiAl₂O₄尖晶石和NiO-MgO固溶体,导致其难以被还原活化。经MgO改性的Al₂O₃载体不仅具有较大的比表面积,而且与NiO的相互作用强度适中,这有利于NiO的分散和稳定,以其为载体制备的催化剂在较高空速下表现出优异的催化反应活性和稳定性,催化剂连续稳定运行100h不失活。     

Cobalt promoted Ni/MgAl2O4 catalyst in lean methane catalytic oxidation

In the present research, magnesium aluminate spinel was prepared as catalyst support using a novel, facile, and efficient mechanochemical method. The Co-promoted catalysts with 20 wt.% of Ni were fabricated using an impregnation route and the samples were analyzed by the X-ray diffraction (XRD), N₂ adsorption/desorption (BET), temperature-programmed reduction and desorption (H₂-TPR and O₂-TPD), and field emission scanning electron microscopy (FESEM) tests. The results confirmed that all samples have a mesoporous structure with a high specific surface area and the presence of cobalt caused complete CH₄ oxidation at low temperatures, and no side reactions were observed. The results indicated that the 3%Co-20%Ni/MgAl₂O₄ catalyst was the optimal sample among the prepared catalysts, owing to the improvement of reduction features and oxygen mobility. The 50 and 90% of methane conversion was obtained at 530 and 600 °C, respectively. Also, the influence of calcination temperature, GHSV, and feed ratio was determined on the catalytic activity. The obtained outcomes revealed that the calcination temperature has a significant effect on the textural properties and catalytic efficiency. The sample calcined at 700 °C showed the weakest performance, which was related to the sintering of particles at high temperatures. The catalytic stability showed that the 3%Co-20%Ni/MgAl₂O₄ has acceptable stability during 600 min time of reaction.

Graphical abstract

     

Performance of Co/MgO catalyst for CO_2 reforming of toluene as a model compound of tar derived from biomass gasification

Catalytic performances of the CO2 reforming of toluene on Co/Mg O catalysts with different cobalt loadings were evaluated in a fluidized-bed reactor. The results showed that the conversion of toluene and the stability of Co/Mg O increased, but the apparent reaction rate decreased at the initial stage with increasing the amount of metallic Co formed from the reduction of Co/Mg O catalysts at 700°C. The deactivation of Co/Mg O catalysts was mainly resulted from that a part of the metallic Co was oxidized by CO2 and could not be re-reduced by H2 at reaction temperature. Therefore, the excess metallic Co on the higher Co loading catalysts was beneficial to the catalyst stability.     

Syngas production from methane steam reforming and dry reforming reactions over sintering-resistant Ni@SiO2 catalyst

Research on Chemical Intermediates - Syngas is a very important intermediate in chemical industry for energy chemicals production through F–T synthesis. Methane steam reforming (MSR) and dry...     

Catalytic steam methane reforming enhanced by CO_2 capture on CaO based bi-functional compounds

Sorption enhanced steam methane reforming(SE-SMR) was performed to maximize hydrogen production and contemporary remove CO_2 from the product stream using bi-functional sorbent-catalyst compounds.Samples were tested at two different scales: micro and laboratory. The CaO amount varied in the CaO-Ca_(12)Al_(14)O_(33) sorbent system synthesized by wet mixing(CaO content of 100 wt%, 56 wt%, 30 wt%, or 0 wt% and balance of Ca_(12)Al_(14)O_(33)) which were upgraded to bi-functional compounds by impregnation of 3 wt% of Ni. Nitrogen adsorption(BET/BJH), X-Ray Diffraction(XRD), Temperature-Programmed Reduction(TPR) and Scanning and Transmission Electronic Microscopy(SEM and TEM, respectively) analyses were performed to characterize structural and textural properties and reducibility of the bi-functional materials and evaluate their catalytic behavior. A fixed sorbent composition CaO-Ca_(12)Al_(14)O_(33)(56 wt% of CaO and Ca_(12)Al_(14)O_(33) balance), was chosen to study the effect of different weight hourly space times(WHST) and CH_4 stream compositions in SE-SMR activity. Impregnated mayenite at both micro and laboratory scales showed stable H_2 content of almost 74%, with CH_4 conversion of 72% similarly to the values reported by the sample containing 30 wt% of CaO in the post-breakthrough.Sample with 30 wt% of CaO showed promisingly behavior, enhancing H_2 content up to almost 94.5%.When the sorption enhanced reaction is performed roughly 89% of CH_4 conversion is achieved, and after the pre-breakthrough, the catalyst worked at the thermodynamic level. During cycling sorption/regeneration experiments, even if CO_2 removal efficiency slightly decreases, CH_4 conversion and H_2 yield remain stable.     

Dramatic improvement of catalyst life by rhodium and cerium additives for Ni-based reforming catalysts

Rhodium and cerium were found to be suitable additives for improving the sulfur-tolerance of Ni-based gasoline reforming catalysts. In these cases, the Rh content was only 0.1 wt.% with 5 wt.% of Ce. The lifetime of Rh-Ce-modified Ni-based catalyst is found to be above 600 hours at 1023K, which is over a ten times longer lifetime than that of the unmodified catalysts, when premium gasoline was used.     

Syngas production from methane dry reforming over Ni/Al2O3 catalyst

Research on Chemical Intermediates - We evaluated dry reforming of methane in a tubular fixed-bed reactor at various reaction temperatures from 923 to 973 K using different reactant...     

Studies on the structure and catalytic performance of S and P promoted Na-W-Mn-Zr/SiO2 catalyst for oxidative coupling of methane

A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). From the characterization results, it is found that the addition of S and P to the Na-W-Mn-Zr/SiO2 catalyst helps the formation of active phases, such as α-cristo...     

Effects of oxidation pretreatment temperature on Kovar used as CO_2 reforming catalyst

The effect of oxidation pretreatment temperature(500 ~ 1 000 ℃) on the catalytic activity of Kovar applied on hydrocarbon CO2reforming was examined. Catalytic performance evaluation using tetradecane at 800 ℃ with 70 μmol/s CO2revealed 700 and 1 000 ℃ as the best pre-oxidation temperature in producing CO and H2,respectively. XRD and SEM-EDX analyses showed that a separate metal oxide layer composed of iron oxide(Fe2O3and F3O4),nickel,cobalt,and possibly their respective oxides started to form when oxidation was conducted at 700 ℃ or higher.The presence of iron enhanced the stability of nickel in the structure while the compact structure of Fe3O4resulted into the formation of a thick and rigid metal oxide layer on the surface of the Kovar tube. The strong physical bond between the metal oxide layer and Kovar tube provided the catalyst good mechanical strength and consequently good catalytic activity.     

煤热解与甲烷蒸汽重整耦合过程焦油在碳基镍催化剂上的原位催化提质（英文）

本研究采用Ni/KD-9催化剂,对CP-SRM过程焦油进行原位催化提质研究。结果表明,在650℃热解温度下,CPSRM在5Ni/KD-9催化作用下的焦油产率为24.4%,略低于不进行催化提质的焦油产率,而轻质焦油产率（18.9%）是未提质时的1.4倍。相比未提质焦油,用5Ni/KD-9提质后焦油中的C₂、C₃和C₄烷基取代苯含量分别增加0.5、0.6和4.0倍;酚和萘的含量也明显提高。采用同位素示踪方法结合典型组分质谱图,探究了催化提质过程的反应机理。结果表明,5Ni/KD-9可以同时催化焦油裂解和甲烷蒸汽重整（SRM）,SRM过程产生的小分子自由基,如·CH_x,·H和·OH可以与焦油裂解产生的自由基结合,从而避免焦油的过度裂解。     

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 properties of Mg-modified Ni-based hexaaluminate catalysts for CO2 reforming of methane to synthesis gas

CO₂ reforming of CH₄ over hexaaluminates LaNi _x Mg_1−x Al₁₁O_19+δ and LaNi _x Mg_0.8Al_11.2−x O_19+δ were studied. XRD analysis confirmed that modifier Ni as well as Mg was inlaid into the hexaaluminate lattice. Hexaaluminate LaNi _x Mg_1−x Al₁₁O_19+δ (1.0 ≥ x ≥ 0.4) showed better catalytic activities and higher resistance to carbon deposition, which was attributed to their pure magnetoplumbite-type structure. For this reaction, x-value between 0.6 and 0.4 was the most suitable.     

Synthesis of 2-methylpyrazine from cyclocondensation of ethylene diamine and propylene glycol over promoted copper catalyst

The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.     

氮化SBA-16负载镍基催化剂的制备及其对甲烷二氧化碳重整反应的催化性能

通过软模板法合成了SBA-16分子筛,采用高温氨气氮化的方法使有序介孔硅材料中的氧原子部分被氮原子取代,得到氮化的SBA-16载体(SBA-16-N)。采用满孔浸渍法制备了镍基催化剂,并将制得的Ni/SBA-16和Ni/SBA-16-N催化剂用于甲烷二氧化碳重整反应。通过透射电镜、氮气物理吸附、X射线衍射、X射线光电子能谱和二氧化碳程序升温脱附等手段研究了载体和催化剂的结构,并利用热重分析对反应之后回收催化剂进行了表征。结果表明,高温氮化后的分子筛中掺入了氮元素,增加了载体的碱性,改善了载体对反应气体的吸附活化能力,增强了载体与金属之间的相互作用,从而提高了催化剂的活性和抗积炭性能。     

Low-temperature utilization of CO_2 and CH_4 by combining partial oxidation with reforming of methane over Ru-based catalysts

Combination of partial oxidation of methane (POM) with carbon dioxide reforming of methane (CRM) has been studied over Ru-based catalysts at 550℃.POM,CRM and combined reaction were performed over 8wt%Ru/γ-Al2O 3 and the results show that both POM and CRM contribute to the combined reaction,between which POM plays a more important role.Moreover,the addition of Ce to Ru-based catalyst results in an improvement in the activity and CO selectivity under the adopted reaction conditions.The Ce-doped catalyst was characterized by N2 adsorption-desorption,SEM,XRD,TPR,XPS and in situ DRIFTS.The mechanism has been studied by in situ DRIFTS together with the temperature distribution of catalyst bed.The mechanism of the combined reaction is more complicated and it is the combination of POM and CRM mechanisms in nature.The present paper provides a new catalytic system to activate CH4 and CO2 at a rather low temperature.     

Atomically-dispersed catalyst by solid-liquid phase transition for CO_2 electroreduction

正The electrochemical reduction of carbon dioxide(CO_2) to value-added fuels and chemicals provides a promising way to realize sustainable carbon recycling [1]. Developing robust electrocatalysts with high activity and selectivity is critically important for efficient electrochemical CO_2 reduction reaction(CO_2RR). Generally, it is challenging to achieve high efficiency and selectivity simultaneously in the CO_2RR due to the multi-proton/electron transfer processes and complex reaction intermediates.     

Effectively promoted catalytic activity by adjusting calcination temperature of Ce-Fe-Ox catalyst for NH3-SCR

A series of Ce-Fe-O_x catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NO_x by NH₃. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-O_x, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-O_x. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NO_x conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe³⁺ active species, higher Ce³⁺ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst.     

SiO2和Al2O3负载的Ni基催化剂在甲烷干重整中的催化性能差异

CH₄与CO₂干重整反应对于环境保护和天然气资源的合理利用具有重要意义。SiO₂和Al₂O₃是适用于甲烷干重整反应的两种典型的催化剂载体。为了阐明这两种载体对催化剂性能的影响,本研究采用等体积浸渍法制备了Ni/Al₂O₃和Ni/SiO₂催化剂,并利用BET、TEM、H₂-TPR、XRD、TG和Raman等技术对还原和反应后的催化剂进行了表征。结果表明,由于载体的性质不同,Ni基催化剂在甲烷干重整中的催化性能也不同。Ni/SiO₂催化剂的初始活性较高,但由于其金属-载体相互作用较弱,催化稳定性较差,在800℃下反应15h其催化活性急剧下降;较弱的金属-载体相互作用使得Ni/SiO₂催化剂上的Ni颗粒较大,有利于积炭前驱物种的生成,导致催化剂快速失活。而对于Ni/Al₂O₃催化剂,金属-载体相互作用较强,Ni颗粒较小,但由于Ni与Al₂O₃生成了NiAl_xO_y物种,有效活性位减少,其催化活性相对较低,但催化稳定性较好,干重整反应进行50h其活性保持稳定;Ni与Al₂O₃之间较强的相互作用有利于形成小且稳定的Ni粒子,能减少积炭,因而具有优异的催化稳定性。