Mesoporous Nickel–Alumina Catalysts for Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG)

Recent progress on the mesoporous nickel–alumina catalysts for hydrogen production by steam reforming of liquefied natural gas (LNG) was reported in this review. A number of mesoporous nickel–alumina composite catalysts were prepared by a single-step surfactant-templating method using cationic, anionic, and non-ionic surfactant as structure-directing agents for use in hydrogen production by steam reforming of LNG. For comparison, nickel catalysts supported on mesoporous aluminas were also prepared by an impregnation method. The effect of preparation method and surfactant identity on physicochemical properties and catalytic activities of mesoporous nickel–alumina catalysts in the steam reforming of LNG was investigated. Regardless of preparation method and surfactant identity, nickel oxide species were finely dispersed on the surface of mesoporous nickel–alumina catalysts through the formation of surface nickel aluminate phase. However, nickel dispersion and nickel surface area of mesoporous nickel–alumina catalysts were strongly affected by the preparation method and surfactant identity. It was found that nickel surface area of mesoporous nickel–alumina catalyst served as one of the important factors determining the catalytic performance in hydrogen production by steam reforming of LNG. Among the catalysts tested, a mesoporous nickel–alumina composite catalyst prepared by a single-step non-ionic surfactant-templating method exhibited the best catalytic performance due to its highest nickel surface area.     

CeO_2/Ni/Mo/SBA-15甲烷二氧化碳重整催化剂的表征和催化性能(英文)

考察了CeO2修饰及未修饰的Ni/Mo/SBA-15催化剂在CH4-CO2重整上的催化性能并采用N2吸脱附、CO2程序升温脱附、H2程序升温还原、傅里叶红外光谱、X射线衍射、扫描电子显微镜和X射线光电子能谱对催化剂进行了表征.结果表明,在常压,800oC条件下,经过100h在线评价后,Ni/Mo/SBA-15和CeO2/Ni/Mo/SBA-15催化剂仍具有高的反应活性和规整的六方介孔结构,其中CeO2修饰的CeO2/Ni/Mo/SBA-15催化剂表面没有积炭形成,表明CeO2的加入促进了Ni物种在SBA-15介孔分子筛表面的分散,从而阻止了Ce/Ni/Mo/SBA-15催化剂上Ni的烧结和积炭.     

High-resolution electron tomography study of an industrial Ni-Mo/gamma-Al2O3 hydrotreating catalyst

The growing demand for high-quality transportation fuels requires their cost-effective production by hydrodesulfurization of crude oils using heterogeneous catalysts. To study the three-dimensional (3D) structure of such a commercial, sulfided Ni-Mo/gamma-Al2O3 catalyst, electron tomography was applied. The MoS2 particles form an interconnected complex structure within the mesopores of the alumina support. Spatial organization, morphology, and orientation of the MoS2 particles in the pores were resolved with sufficient accuracy to display the 6-A-spaced MoS2 crystal planes. The proximity of the MoS2 edge planes and more loosely interacting MoS2 basal planes to the alumina support showed the presence of pores smaller than 3 nm, which was confirmed by physisorption experiments. The actual shape of the MoS2 particles cannot be described by simple models as derived from studies on model catalysts. Electron tomography is a unique tool to study the actual 3D structure of complex industrial catalysts with sub-nanometer resolution.     

Development of Highly Active Co(Ni)Mo Catalysts for the Hydrodesulfurization of Dibenzothiophene Compounds

Co- or Ni-promoted Mo sulfide catalysts were prepared by combining three methods, sonochemical synthesis of Mo sulfides, promoter addition by chemical vapor deposition (CVD), and fluorination of alumina support, to improve their performance in the hydrodesulfurization (HDS) process. Sonochemically synthesized Mo sulfides exhibited higher HDS activity, particularly for the hydrogenation (HYD) of dibenzothiophene (DBT) compounds, than in the case of the catalysts prepared by impregnation due to the improved dispersion of the Mo species. The addition of Co or Ni to the catalyst by a CVD method allowed the selective decoration of the Mo-sulfide surface with the promoter and accordingly produced greater amounts of the Co–Mo–S and Ni–Mo–S phases, which are known to be active sites for HDS. The performance of catalysts prepared by combining sonochemical and CVD methods was further improved by the addition of fluorine, which generated Brönsted acid sites that were responsible for the HYD route and also for the migration of methyl groups in 4,6-dimethyldibenzothiophene (4,6-DMDBT).     

Hydroconversion of Oxidation Products of Sulfur-Containing Aromatic Compounds

Hydroconversion of benzo- and dibenzothiophene sulfone on a Ni–Mo sulfide catalyst based on mesoporous aluminosilicate Al-HMS and on unsupported catalysts prepared in situ in the course of decomposition of poorly soluble precursors (molybdenum hexacarbonyl, nickel naphthenate) was studied. Hydrogenation of sulfones was perfpormed at 250, 340, and 380°С and elevated СО pressure in the presence of water ensuring in situ generation of hydrogen via water-gas shift reaction.     

Hydrogen Production by Steam Reforming of Ethanol Over Mesoporous Ni–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> Catalysts

This review paper reports the recent progress concerning the application of nickel–alumina–zirconia based catalysts to the ethanol steam reforming for hydrogen production. Several series of mesoporous nickel–alumina–zirconia based catalysts were prepared by an epoxide-initiated sol–gel method. The first series comprised Ni–Al₂O₃–ZrO₂ xerogel catalysts with diverse Zr/Al molar ratios. Chemical species maintained a well-dispersed state, while catalyst acidity decreased with increasing Zr/Al molar ratio. An optimal amount of Zr (Zr/Al molar ratio of 0.2) was required to achieve the highest hydrogen yield. In the second series, Ni–Al₂O₃–ZrO₂ xerogel catalysts with different Ni content were examined. Reducibility and nickel surface area of the catalysts could be modulated by changing nickel content. Ni–Al₂O₃–ZrO₂ catalyst with 15 wt% of nickel content showed the highest nickel surface area and the best catalytic performance. In the catalysts where copper was introduced as an additive (Cu–Ni–Al₂O₃–ZrO₂), it was found that nickel dispersion, nickel surface area, and ethanol adsorption capacity were enhanced at an appropriate amount of copper introduction, leading to a promising catalytic activity. Ni–Sr–Al₂O₃–ZrO₂ catalysts prepared by changing drying method were tested as well. Textural properties of Ni–Sr–Al₂O₃–ZrO₂ aerogel catalyst produced from supercritical drying were enhanced when compared to those of xerogel catalyst produced from conventional drying. Nickel dispersion and nickel surface area were higher on Ni–Sr–Al₂O₃–ZrO₂ aerogel catalyst, which led to higher hydrogen yield and catalyst stability over Ni–Sr–Al₂O₃–ZrO₂ aerogel catalyst.     

Synthesis of nanostructured carbon on Ni catalysts supported on mesoporous silica,preparation of carbon-containing adsorbents,and preparation and study of lipase-active biocatalysts

This work continues a series of our studies on the synthesis of nanostructured carbon (NSC) by the pyrolysis of H₂ + C₃–C₄ alkane mixtures on nickel and cobalt metal catalysts supported on chemically diverse inorganic materials (aluminosilicates, alumina, carbon) having different textural characteristics (mesoporous and macroporous supports) and shapes (granules, foamed materials, and honeycomb monoliths). Here, we consider Ni catalysts supported on granular mesoporous silica (SiO₂). It has been elucidated how the yield of synthesized carbon depends on the Ni/SiO₂ catalyst preparation method (homogeneous precipitation or impregnation) and on the composition of the impregnating solution, including the molar ratio of its components—nickel nitrate and urea. The morphology of catalytic NSC and Ni distribution in the silica granule have been investigated using a scanning electron microscope with an EDX analyzer. Carbon-containing composite supports (NSC/SiO₂) have been employed as adsorbents for immobilizing microbial lipase. The enzymatic activity and stability of the resulting biocatalysts have been estimated in transesterification reactions of vegetable (sunflower and linseed) oils involving methyl or ethyl acetate, esterification, and synthesis of capric acid–isoamyl alcohol esters in nonaqueous media.     

Performance of the ρ- Al2O3 based Ag promoted Pd/ Al2O3 catalyst during Acetylene hydrogenation with an ideal feed

Catalytic hydrogenation of acetylene was studied with an ideal feed with a catalyst prepared from different alumina support and with varying quantities of promoter addition. Silver promoted palladium alumina catalysts were prepared on the transition alumina, ρ-alumina and the catalyst performance was compared with the traditional palladium alumina catalyst based on α-alumina. The catalyst supports were prepared using the granulation technique and sequential impregnation method was used for the catalyst preparation. The silver metal loading was varied in the catalysts and the impact of varied promoter quantity was also studied. The supports were characterized for the acidity, alumina phase, and catalyst characterization was done using TEM, TPR, and BET method to understand the difference between catalysts prepared on different types of alumina support. A fixed bed catalyst reaction was used for the performance evaluation and an ideal gas with acetylene and nitrogen was used as the feed. The catalyst evaluation gives the comparative performance of the catalysts at different temperature conditions. Acetylene conversion and ethylene selectivity in the product were evaluated. The spent catalyst analysis was done using TGA and CHN analysis was performed to understand the carbon deposition and by-product formation during the reaction with different types of catalysts.     

Production of hydrogen-rich gas and multi-walled carbon nanotubes from ethanol decomposition over molybdenum modified Ni/MgO catalysts

A series of molybdenum modified Ni/MgO catalysts(Ni-Mo/MgO) with different loading ratios of Ni : Mo were prepared by impregnation method. Ethanol decomposition to co-produce multi-walled carbon nanotubes and hydrogen-rich gas at temperatures of 600–800 ℃ was investigated over the synthesized Ni-Mo/MgO catalysts. The results showed that the catalytic activity depended strongly on the reaction temperature and loading ratio of Ni : Mo. According to the gaseous and solid products obtained, the reaction pathways for ethanol decomposition were suggested.     

Multilayered catalysts for fatty acid ester hydrotreatment into fuel range hydrocarbons

This study aims to investigate Ni–Mo/γAl₂O₃ and Ni–La/Zn-ZSM-5–γAl₂O₃ catalysts, which convert methyl esters into various compounds with a similar composition to those found in diesel fuels. The catalysts were synthesized by impregnation using two different routes and characterized by atomic absorption spectrometry, Brunauer–Emmett–Teller, and scanning electron microscopy. The acid strength distribution indicates a relatively high concentration of weak acid centers for both materials. The disposal of the catalysts into the reactor system is an important factor for driving the process toward the desired reaction products. The hydrodeoxygenation becomes important and paraffins are formed as intermediaries when Ni–Mo/γAl₂O₃ is first disposed into the reactor, whereas hydrocracking is poor and the dehydrocyclization does not occur in the case of Ni–La/Zn-ZSM-5–γAl₂O₃ as first layer. Triple-layered catalytic systems enhance the production of n-paraffins with high carbon number, mainly C17 and C18, which are important as diesel component. The effect of temperature was also studied and it was found that aromatics are mainly formed over double-layered catalytic systems by varying the temperature. In the case of triple-layered catalysts, the change in the product composition from saturated hydrocarbons with 12–18 carbon atoms to aromatics was observed by increasing the temperature from 420 to 445 °C. An interesting finding by the addition of n-octane in the feed was observed and the considerable increase in C8 aromatics involved the dehydrocyclization that occurred faster than hydrocracking.     

介孔Ni/MgO催化剂催化水蒸气重整生物质油制氢

采用水热法制备了介孔MgO作为催化剂的载体,并制备了介孔Ni/MgO催化剂。利用N_2吸附-脱附、XRD、H_2-TPR等对样品进行表征,并考察了介孔Ni/MgO催化水蒸气重整糠醛、生物质油模型物和两种商用生物质油制氢的活性。结果表明,在介孔Ni/MgO催化剂催化水蒸气重整糠醛制氢反应中,随着反应温度的提高,水蒸气重整糠醛中糠醛的转化率、氢气的产率和氢气的选择性,都呈现递增的趋势。在反应温度提高到600℃时,糠醛的转化率和氢气的产率分别达到94.9%和83.2%。Ni/MgO催化水蒸气重整二组分模拟生物质油,糠醛/乙酸、糠醛/羟基丙酮制氢的反应中,氢气的产率分别达到87.3%和86.8%,均高于水蒸气重整糠醛反应中氢气的产率。由此表明,乙酸或羟基丙酮的存在,提高了模拟生物质油中主要有机物组分糠醛的转化率,并相应地提高了氢气的产率。在水蒸气重整商用生物质油制氢反应中,随着反应物水碳比(S/C(molar ratio)=5、10、15、20、25)的提高,主要有机物的转化率、氢气的产率和选择性呈现出增加的趋势。在水碳比为20时,两种生物质油的主要有机物组分(糠醛、乙酸和羟基丙酮)的转化率均可达90%以上,氢气的产率也达到81.0%以上。由此可知,Ni催化剂对于水蒸气重整商用生物质油也具有较高的催化活性。     

Mo对Ni/ZnO催化乙醇水蒸气重整制氢性能的影响

考察了Mo及温度对Ni/ZnO催化乙醇水蒸气重整制氢的活性、选择性和抗积炭性能的影响。结果表明，773K适量添加Mo能提高Ni/ZnO催化剂的活性和氢气选择性；Ni/ZnO及Ni-Mo/ZnO催化剂的活性随着温度的升高而提高，823K乙醇完全转化；873K时，Mo质量分数为0.83%的Ni-Mo/ZnO催化剂对氢气的选择性最高；添加Mo可以提高Ni/ZnO催化剂的抗积炭能力，从而提高该催化剂的稳定性。程序升温还原（TPR）和X射线衍射（XRD）结果表明，添加Mo有利于Ni氧化物在载体上的分散；减弱氧化态镍物种与载体之间的作用，从而提高了催化剂的活性、选择性和稳定性。     

Mesoporous Molecular Sieves as Advanced Supports for Olefin Metathesis Catalysts

Summary: Siliceous mesoporous molecular sieves MCM-41, MCM-48 and SBA-15 and organised mesoporous alumina represent progressive supports for new heterogeneous catalysts for olefin metathesis and metathesis polymerization. In combination with Mo and Re oxides they provide catalysts of considerably higher activity in comparison with those based on conventional silica and alumina. Immobilization of Mo and Ru alkylidenes on these materials led to the highly active and selective catalysts with negligible leaching of transition metal.     

Carbon dioxide reforming of methane over Ni/Mo/SBA-15-La2O3 catalyst: Its characterization and catalytic performance

The Ni/Mo/SBA-15 catalyst was modified by La2O3 in order to improve its thermal stability and carbon deposition resistance during the CO2 reforming of methane to syngas. The catalytic performance, thermal stability, structure, dispersion of nickel and carbon deposition of the modified and unmodified catalysts were comparatively investigated by many characterization techniques such as N2 adsorption, H2-TPR, CO2-TPD, XRD, FT-IR and SEM. It was found that the major role of La2O3 additive was to improve the pore structure and inhibit carbon deposition on the catalyst surface. The La2O3 modified Ni/Mo/SBA-15 catalyst possessed a mesoporous structure and high surface area. The high surface area of the La2O3 modified catalysts resulted in strong interaction between Ni and Mo-La, which improved the dispersion of Ni, and retarded the sintering of Ni during the CO2 reforming process. The reaction evaluation results also showed that the La2O3 modified Ni/Mo/SBA-15 catalysts exhibited high stability.     

Characterization of the active phase of NiMo/Al2O3 hydrodesulfurization catalysts

The active phase of the NiMo/Al₂O₃ catalyst for hydrodesulfurization reactions has been investigated in this work. Special attention has been focused on the effect of the order of metal impregnation on the formation of the active phase in the reaction. The Mo and Ni oxides and their sulfides on the alumina were investigated by XPS and DRS analyses. The Ni-Mo oxides or precursor of the active phase which are chemically bonded between Mo and Ni were also confirmed from the binding energy shifts of the XPS peaks. The amount of Ni-Mo oxides was determined after the formation of metal oxides during calcination. The Ni-Mo sulfide (active phase) was then induced through sulfidation. It was important that Mo should be located at the tetrahedral sites on the alumina with a high Mo dispersion. These results indicated that there are two important factors in preparing highly efficient Ni-Mo catalysts; one is that Mo should be located at the tetrahedral coordination on Al₂O₃ in high dispersion (Mo/Al₂O₃) and the other is that the Ni species should be supported on MoAl₂O₄ to form Ni-Mo oxides which change into the Ni-Mo sulfide active sites by sulfidation.     

Oxidative addition of dihydrogen to the bimetallic sulfide catalysts: evidence by X-ray photoelectron spectroscopy

Reversible transformations Ni(IV)↔Ni(II) in alumina and Sibunit supported (Ni,Mo) sulfide catalysts were observed after in situ thermal treatment of catalysts in an X-ray photoelectron spectrometer chamber. The phenomenon is interpreted as a reductive elimination of occluded hydrogen under low pressure and high temperature, and oxidative addition of hydrogen after catalyst treatment with an (H₂+H₂S) mixture.     

Hierarchical Structure of NiMo Hydrodesulfurization Catalysts Determined by Ptychographic X-Ray Computed Tomography

Hydrodesulphurization, the removal of sulphur from crude oils, is an essential catalytic process in the petroleum industry safeguarding the production of clean hydrocarbons. Sulphur removal is critical for the functionality of downstream processes and vital to the elimination of environmental pollutants. The effectiveness of such an endeavour is among other factors determined by the structural arrangement of the heterogeneous catalyst. Namely, the accessibility of the catalytically active molybdenum disulphide (MoS₂) slabs located on the surfaces of a porous alumina carrier. Here, we examined a series of pristine sulfided Mo and NiMo hydrodesulphurization catalysts of increasing metal loading prepared on commercial alumina carriers using ptychographic X-ray computed nanotomography. Structural analysis revealed a build consisting of two interwoven support matrix elements differing in nanoporosity. With increasing metal loading, approaching that of industrial catalysts, these matrix elements exhibit a progressively dissimilar MoS₂ surface coverage as well as MoS₂ cluster formation at the matrix element boundaries. This is suggestive of metal deposition limitations and/ or catalyst activation and following prohibitive of optimal catalytic utilization. These results will allow for diffusivity calculations, a better rationale of current generation catalyst performance as well as a better distribution of the active phase in next-generation hydrodesulphurization catalysts.     

山西芮城永乐宫元代天花、藻井研究*

采用不同方法制备了一系列Ni/Al_2O_3催化剂,在无NH_3、无碱条件下对其己二腈催化加氢制1,6-己二胺的反应性能进行研究.通过XRD、 BET、 TEM、 XPS及程序升温实验等结果表明,采用沉淀剂有利于细小Ni纳米颗粒在催化剂介孔内的分散。然而较强的Ni与载体间相互作用不利于氢气的吸附活化,还原处理后催化剂中仍存在较高含量的氧化态Ni物种.采用浸渍法制备的Ni/Al_2O_3-I催化剂中颗粒的平均尺寸为18.5 nm, Ni颗粒暴露在载体表面,生成较高含量的还原态Ni0物种及有利于反应物吸附的中等强度酸性位点.该Ni/Al_2O_3-I催化剂表现出优良的低温活性,在60℃时,己二腈转化频率(TOF)可达39.7 h~(-1);80℃时转化率为100%, 1,6-己二胺收率可达73.0%.然而,由于Ni/Al_2O_3-I催化剂中Ni与Al_2O_3间相互作用较弱,经过3次循环性能测试,催化剂活性明显下降.进一步以少量Cu元素修饰低含量Ni/Al_2O_3-I催化剂, Cu助剂的引入有效改善了Ni纳米颗粒的分散性,并与部分Ni组分形成双金属纳米颗粒.Ni_(15)Cu_3/Al_2O_3催化剂经5次循环反应后无明显失活现象,催化剂的形貌及化学结构亦无明显变化, Cu的引入在保持Ni基催化剂低温活性的同时有效提升了催化剂的循环稳定性,催化剂的TOF为52.1 h~(-1).     

Roads less traveled: Nitrogen reduction reaction catalyst design strategies for improved selectivity

Direct electrochemical nitrogen reduction for ammonia production is necessary to reduce the use of fossil fuels from conventional Haber–Bosch methods. Applications of nitrogen reduction electrocatalysts remain inhibited by slow reaction kinetics and low faradaic efficiencies because of competitive H₂ production pathways. Current strategies to address this challenge in selectivity have focused on catalyst design, reactor configuration, and electrolyte conditions. This brief review discusses the thermodynamic and kinetic challenges in the field as well as current underused approaches for selective catalyst development including bimetallic catalysts, transition metal nitrides, and carbon supports.     

Ordered Mesoporous NiCeAl Containing Catalysts for Hydrogenolysis of Sorbitol to Glycols

Cellulose-derived sorbitol is emerging as a feasible and renewable feedstock for the production of value-added chemicals. Highly active and stable catalyst is essential for sorbitol hydrogenolysis. Ordered mesoporous M–xNiyCeAl catalysts with different loadings of nickel and cerium species were successfully synthesized via one-pot evaporation-induced self-assembly strategy (EISA) and their catalytic performance were tested in the hydrogenolysis of sorbitol. The physical chemical properties for the catalysts were characterized by XRD, N₂ physisorption, H₂-TPR, H₂ impulse chemisorption, ICP and TEM techniques. The results showed that the ordered mesopores with uniform pore sizes can be obtained and the Ni nanoparticles around 6 nm in size were homogeneously dispersed in the mesopore channels. A little amount of cerium species introduced would be beneficial to their textural properties resulting in higher Ni dispersion, metal area and smaller size of Ni nanoparticles. The M–10Ni2CeAl catalyst with Ni and Ce loading of 10.9 and 6.3 wt % shows better catalytic performance than other catalysts, and the yield of 1,2-PG and EG can reach 56.9% at 493 K and 6 MPa pressure for 8 h after repeating reactions for 12 times without obvious deterioration of physical and chemical properties. Ordered mesoporous M–NiCeAl catalysts are active and stable in sorbitol hydrogenolysis.