Selective CO methanation over amorphous Ni-Ru-B/ZrO2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO₂ catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni₆₁Ru₉B₃₀/ZrO₂ catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230°C～250°C, and the CO₂ conversion was kept under the level of 0.9%.     

Influence of Composition of Nickel-Iron Nanoparticles for Abiotic CO2 Conversion to Early Prebiotic Organics

Abiotic synthesis of formate and short hydrocarbons takes place in serpentinizing vents where some members of vent microbial communities live on abiotic formate as their main carbon source. To better understand the catalytic properties of Ni−Fe minerals that naturally exist in hydrothermal vents, we have investigated the ability of synthetic Ni−Fe based nanoparticular solids to catalyze the H₂-dependent reduction of CO₂, the first step required for the beginning of pre-biotic chemistry. Mono and bimetallic Ni−Fe nanoparticles with varied Ni-to-Fe ratios transform CO₂ and H₂ into intermediates and products of the acetyl-coenzyme A pathway—formate, acetate, and pyruvate—in mM range under mild hydrothermal conditions. Furthermore, Ni−Fe catalysts converted CO₂ to similar products without molecular H₂ by using water as a hydrogen source. Both CO₂ chemisorption analysis and post-reaction characterization of materials indicate that Ni and Fe metals play complementary roles for CO₂ fixation.     

Hydrogen production by glycerol reforming in supercritical water over Ni/MgO-ZrO2 catalyst

Nano ZrO₂ and MgO-ZrO₂ were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water (SCW). The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600–800 °C. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO₂ catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H₂/mol of glycerol could be obtained.     

Ru/Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> catalysts for steam reforming of methane: effects of Ru content on self-activation property

The effects of Ru on the self-reducibility of Ru-doped Ni/MgAl₂O₄ catalysts, which do not need pre-reduction treatment with H₂, were investigated in the steam reforming of methane (SRM). The Ru-promoted Ni/MgAl₂O₄ catalysts with various amounts of Ru (0–0.5 wt%) were prepared by stepwise impregnation and co-impregnation methods using hydrotalcite-like MgAl₂O₄ support. For comparison, Ru/MgAl₂O₄ catalysts with the same amount of Ru were also prepared by the impregnation method. The catalysts were characterized by the N₂-sorption, XRD, H₂-TPR, H₂-chemisorption, and XPS methods. Ni/MgAl₂O₄ catalyst in the presence of even the trace amount of Ru (Ru content ≥0.05 wt%) showed higher conversion without pre-reduction as compared to Ru/MgAl₂O₄ catalysts in SRM under the same conditions. The self-activation of Ru–Ni/MgAl₂O₄ catalysts is mainly attributed to the spillover of hydrogen, which is produced on Ru at first and then reduces NiO species under reaction conditions. Besides, Ru doping makes the reduction of NiO easier. The stepwise impregnated Ru/Ni/MgAl₂O₄ catalyst produced superior performance as compared to co-impregnated Ru–Ni/MgAl₂O₄ catalyst for SRM.     

载体表面氧化程度对Ni/SiC甲烷化催化剂性能的影响

采用等体积浸渍法制备了Ni/SiC甲烷化催化剂, 研究了SiC载体表面氧化程度对催化剂低温活性和高温稳定性的影响, 并采用热重-差示扫描量热、N₂物理吸附、傅立叶变换红外光谱、氨程序升温脱附、X射线衍射、氢程序升温还原和氢化学吸附技术对样品进行了表征. 结果表明, 随着载体氧化温度的提高, 催化剂的比表面积和镍分散度降低, 但还原性和反应稳定性提高. 未氧化载体所负载催化剂的高温稳定性最差, 其原因在于载体对镍粒子的固定作用最弱. 负载于500和700℃处理的SiC载体上的催化剂具有较好的低温活性和高温稳定性, 这是因为适度氧化后的载体能较好地分散并固定镍粒子. 900℃处理的载体因过度氧化形成了低活性的氧化层, 使负载的镍粒子变大, 因而催化剂的低温活性最差.     

原位合成的Cu-SSZ-13催化剂：结晶时间对NH3-SCR性能的影响

通过一步法原位合成Cu-SSZ-13分子筛催化剂,考察了结晶反应时间对NH3选择性催化还原(NH3-SCR)催化性能的影响,利用H2程序升温还原(H2-TPR)、X射线衍射(XRD)、电子顺磁共振光谱(EPR)和X射线电子能谱(XPS)等分析手段表征催化剂。结果表明,结晶时间不同会影响到Cu-SSZ-13分子筛中活性Cu物种的含量和分布,结晶时间为4 d时Cu-SSZ-13分子筛的NH3-SCR催化性能最佳。高温水热条件下,Cu-SSZ-13分子筛中不稳定的Cu~(2+)A物种会发生迁移而形成相对稳定的Cu~(2+)B物种;Cu~(2+)物种发生团聚而造成分子筛结构破坏,部分Cu~(2+)物种也因分子筛骨架坍塌而被包埋,这是导致催化活性下降的主要原因。     

One-pot three-component synthesis of bis(indolyl)methanes under solvent-free condition using heteropoly-11-tungsto-1-vanadophosphoric acid supported on natural clay as catalyst

One-pot three-component condensation reaction of two moles of indole and one mole of aromatic aldehyde for the synthesis of bis(indolyl)methanes in the presence of new catalytic material, heteropoly-11-tungsto-1-vanadophosphoric acid, H₄[PV^VW₁₁O₄₀] (HPV) supported on activated natural clay under solvent-free reaction condition has been proposed. The catalysts were prepared by incipient wetness impregnation method. The physicochemical characterizations of the HPV (20%) supported on natural clay (HPVAC-20) have also been discussed. Solvent-free heterogeneous reaction condition, simple workup procedure, short reaction time, high yield of products, and reusability of the catalyst are the advantages of the protocol.     

镍基催化剂上稻草水蒸气重整制富氢合成气

采用浸渍法制备了SiO₂, γ-Al₂O₃, CaO和TiO₂负载的Ni催化剂, 以及不同MgO含量的MgO-7.5%Ni/γ-Al₂O₃催化剂,利用X射线衍射和N₂吸附-脱附技术表征了催化剂的结构,在固定床反应器上评价了它们在稻草水蒸气催化重整制合成气反应中的催化性能,考察了反应条件对催化剂性能的影响.结果表明, 以γ-Al₂O₃为载体时Ni催化剂活性最高,其中7.5%Ni/γ-Al₂O₃催化剂的H₂收率可达1071.3ml/g,H₂:CO的体积比为1.4:1;同时,MgO的添加进一步提高了该催化剂的性能,当MgO含量为1.0%时,H₂收率可达1194.6ml/g,H₂:CO体积比可达3.9:1.可见MgO的加入促进了Ni基催化剂上稻草水蒸气催化重整制合成气反应的进行,同时使得合成气中CO发生水-汽转换反应,从而大大提高了合成气中H₂含量.     

The role of urea in Cu–Zn–Al catalysts for methanol steam reforming

Abstract  

Impregnated Cu–Zn over Al₂O₃ exhibits high activity with the use of a lower amount of active metal relative to conventional co-precipitation catalysts. The activity of the catalyst could be enhanced by addition of urea to the metal salt solution during impregnation. The H₂ yield from Cu–Zn catalysts with urea is 42%, while the H₂ yield from catalyst without urea is only 28% in a continuous system at 250 °C and 1.2 atm. The H₂ yield of the catalyst with urea in this study could compete with that of commercial catalysts. The role of urea in the Cu–Zn catalysts was investigated. X-ray diffraction (XRD) analysis of the catalysts shows that the crystal size of CuO could be reduced by the addition of urea. The XRD diffractogram of the catalyst prior to calcination also shows the formation of NH₄NO₃, which could aid in dissociation of metal clusters. Scanning electron microscopy (SEM) images of catalysts show the size of Cu–Zn compound clusters and also their dispersion over the Al₂O₃ surface on the impregnated catalysts. The addition of urea could also yield smaller Cu–Zn compound clusters and better dispersion compared with the impregnated catalyst without urea. Such impregnated Cu–Zn catalysts with urea could be alternative novel catalysts for methanol steam reforming.     

碱金属和碱土金属促进的Ni/SiO2催化剂上甲烷的二氧化碳重整制合成气

Ni/SiO2 catalysts promoted by alkali metals K and Cs or alkaline earth metals Mg, Ca, Sr and Ba were prepared, characterized by H2-TPR and XRD, and used for the production of synthesis gas via methane reforming with CO2. Though K and Cs promoted Ni catalysts could eliminate coke deposition, the reforming activity of these promoted catalysts was decreased heavily. Mg and Ca promoted Ni/SiO2 catalysts exhibited excellent coke resistance ability with minor loss of the reforming activity of Ni/SiO2. Ba showed poor coke resistance ability and small amount of Sr increased the formation of coke. The possible mechanism of these promoters was discussed.     

Synthesis of Nanostructured Carbon on Ni Deposited on Mesoporous Aluminum,and Titanium Oxides. Investigation of Biocatalytic Properties of Lipase Adsorbed on Carbon–Mineral Supports

This work is a continuation of the studies devoted to the synthesis of nanostructured carbon (NSC) as a result of the pyrolysis of a mixture of H₂ + C₃–C₄ alkanes on supported Ni catalysts. Mesoporous alumina (γ-Al₂O₃) and titania (TiO₂), on which Ni(II) compounds are deposited by impregnation or homogeneous precipitation, are studied as carriers. Using the methods of thermogravimetric analysis and scanning electron microscopy, it is shown that the activity of Ni catalysts (carbon yield) and the morphology of synthesized NSC are largely determined by the chemical nature of the support. It is found that the synthesis of NSC in the form of carbon nanofibers with a pronounced filamentary structure proceeds only on a Ni catalyst supported on titanium dioxide. The mesoporous carbon–mineral supports obtained after catalytic pyrolysis were studied in the adsorptive immobilization of the enzyme such as Thermomyces lanuginosus lipase. The adsorption properties of the supports, as well as the enzymatic activity and stability of the prepared biocatalysts in the esterification of saturated fatty acids (capric, C10: 0) with aliphatic alcohols (isopentanol, C₅) in the non-aqueous media of organic solvents (hexane and diethyl ether) at ambient temperature, are studied. Biocatalysts prepared by lipase adsorption on NSC/TiO₂ show the maximum esterification activity of 100 EA/g, which is 20–45 times higher than the activity of lipase adsorbed on NSC/Al₂O₃.     

碱金属助剂类型及前驱物对改性NiAl复合氧化物催化分解N2O活性的影响

制备了不同Ni/Al原子比的NiAl类水滑石样品,焙烧获得NiAl复合氧化物,用于N₂O分解反应,研究了NiAl复合氧化物组成对催化活性的影响。在活性较高的NiAl复合氧化物表面浸渍碱金属碳酸盐溶液,制备改性NiAl复合氧化物,考察了碱金属类型（Na、K、Cs）和钾前驱物（K₂CO₃、K₂C₂O₄、CH₃COOK、KNO₃）对改性催化剂活性的影响。用XRD、ICP-AES、FT-IR、BET、H₂-TPR、XPS技术表征了催化剂的组成结构。结果表明,Ni/Al原子比为2.7的NiAl复合氧化物催化活性较高;Na、K、Cs碳酸盐改性NiAl复合氧化物均提高了催化剂活性,其中K的助剂效应最强。钾前驱物对K改性NiAl复合氧化物的催化活性有显著影响,其中碳酸钾、醋酸钾、草酸钾的加入明显提高了改性催化剂的催化活性,而加入硝酸钾反而降低了催化剂活性。     

Study of activated carbon supported iron catalysts for the Fischer-Tropsch synthesis

Summary Characterization (BET and TPD) and reaction studies were conducted with activated carbon supported iron catalysts (Fe/AC) used for the Fischer-Tropsch synthesis (FTS). The TPD study showed that there existed interactions between metals and the AC surface. Greater association of Cu and K promoters with the AC surface resulted in stronger promoter to surface interaction, which enhanced the H₂ desorption ability of the Cu and K promoted Fe/AC catalyst prepared under vacuum impregnation (VI). Catalytic behavior of a Fe/AC catalyst (VI-15 Fe/2 Cu/2 K/81 AC, in parts per weight) was studied in a 1-liter slurry phase continuous stirred tank reactor. The catalyst presented moderate syngas conversion (44.3-60.6%) and high gaseous selectivity (CH₄, 12.8-15.1% and C₂-C₄, 42.4-46.1%) under 304^oC, 3.0 MPa, 1.1 L(STP)/g-cat/h, and H₂/CO = 2.0 during 166 h of testing. Detectable hydrocarbons up to C₁₈ were formed on the Fe/AC catalyst.     

Sorbitol Hydrogenolysis to Glycols over Baisic Additive Promoted Ni-based Catalysts

A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H₂-TPR and CO₂-TPD techniques. It was found that the introduction of basic additives enhanced the basicities of catalyats and promoted the dispersities of Ni particles by strong interaction between Ni²⁺ and basic additives. Among the Ni based catalysts, 10%Ni/10%La₂O₃/ZrO₂ showed the superior performance in sorbitol hydrogenolysis. The synergistic effect of Ni and La₂O₃ was proven to play an essential role in selective synthesis of EG and 1,2-PG. In the optimal reaction condition, the catalyst presented 100% sorbitol conversion and over 48% glycols (EG and 1,2-PG) yield. The kinetics study of polyols (sorbitol, xylitol and glycerol) hydrogenolysis showed that polyols with more hydroxyl number have higher activity and products distribution was final results of kinetic balance, which could give us some inspiration about how to change the products selectivity.     

Effects of metal centers of complexes supported by S,S′-bis(2-pyridylmethyl)-1,2-thioethane on catalytic activities for electrochemical- and photochemical-driven hydrogen production

S,S′-bis(2-pyridylmethyl)-1,2-thioethane (bpte) reacts with MCl₂ (M = Co, Ni, and Fe) to give three complexes, namely, [Co^II(bpte)Cl₂] ( 1 ), [Ni^II(bpte)Cl₂] ( 2 ), and [Fe^II(bpte)Cl₂] ( 3 ), respectively. They all act as catalysts for proton or water reduction to dihydrogen via electrolysis or photolysis. Under an overpotential of 837.6 mV, the electrolysis of a neutral buffer with complex 1 , 2 , or 3 can provide 418 (±3), 555 (±3), and 243 (±3) moles of hydrogen per mole of catalyst per hour (mol H₂/mol catalyst/h), respectively. Under blue light, together with a photosensitizer and ascorbic acid (H₂A) as a sacrificial electron donor, the photolysis of an aqueous solution (pH 4.5) containing complex 1 , 2 , or 3 can afford 9060 (±5), 24,900 (±5), and 10,630 (±5) moles H₂ per mole of catalyst (mol of H₂ [mol of cat]⁻¹) during 83-h irradiation with an average apparent quantum yield of 7.1%, 24%, and 10%, respectively. The results show that the nickel complex [Ni^II(bpte)Cl₂] exhibits a more efficient activity for hydrogen generation than the iron or cobalt species. These findings may offer a new chemical paradigm for the design of efficient catalysts.     

镍磷物质的量比对负载型Ni2P/MCM-41催化剂结构及加氢脱硫性能的影响

以MCM-41为载体,采用一种简捷、温和法制备了负载型Ni₂P/MCM-41催化剂。用H₂程序升温还原(H₂-TPR)、X射线衍射(XRD)、N₂吸附比表面积测定(BET)和X射线光电子能谱(XPS)分析对催化剂进行了表征。以1%(质量分数)二苯并噻吩(DBT)的十氢萘溶液为原料,在连续固定床反应装置上,研究了初始Ni/P物质的量比对催化剂HDS活性的影响,并考察了催化剂的稳定性。结果表明,初始Ni/P物质的量比为1/2和1/3的前驱体,在390 ℃下还原时得到单一的Ni₂P相。初始Ni/P物质的量为1/2时,得到的催化剂活性最好。在反应温度340 ℃、压力3.0 MPa、氢/油体积比500、质量空速2.0 h^-1时,DBT的转化率接近100%。     

High Carbon-Resistance Ni@CeO<Subscript>2</Subscript> Core–Shell Catalysts for Dry Reforming of Methane

Ni@CeO₂ core–shell catalysts were synthesized via a facile surfactant-assisted hydrothermal method and their catalytic performance in the dry reforming of methane (DRM) reaction was evaluated. A variety of techniques including XRD, N₂ adsorption–desorption, SEM, TEM, TPO, TGA were employed to characterize the prepared or spent catalysts. The encapsulation by the CeO₂ shell, on one side, can restrict the sintering and growth of Ni nanoparticles under harsh reaction conditions. On the other side, compared to the conventional shell material of SiO₂, CeO₂ can provide more lattice oxygens and vacancies, which is helpful to suppress coke deposition. Consequently, the Ni@CeO₂ core–shell catalysts exhibited better catalytic activity and stability in the DRM reaction with respect to the referenced Ni@SiO₂ core–shell catalysts and Ni/CeO₂ supported catalysts.     

负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究

采用等体积浸渍法和共沉淀法制备了Ni催化剂,在固定床反应器上考察了Ni负载量、焙烧温度、反应温度等因素对乙二醇低温重整制氢反应活性和选择性的影响。应用X射线衍射、氮物理吸附、H₂程序升温还原等技术对负载型Ni催化剂进行了表征。结果表明,共沉淀法制备的Ni/CeO₂催化剂具有较小的NiO颗粒与CeO₂载体颗粒粒径,催化活性较高。添加少量氧化钴到Ni/CeO₂催化剂中可使H₂收率达72.6%,EG转化率达93.1%。在CeO₂中添加Al₂O₃能提高负载Ni催化剂的活性,乙二醇转化率达94.0%,H₂收率达67.0%;但添加SiO₂则使其活性明显变差。     

Effect of synthesis solution pH of Co/γ-Al_2O_3 catalyst on its catalytic properties for methane conversion to syngas

The cobalt nanoparticles over γ-Al_2O_3 support were prepared via chemical reduction of CoCl_2·6H_2O using NaBH_4 with various values of pH in the range of 11. 92-13. 80. Synthesized catalysts were studied through X-ray diffraction( XRD),N_2 adsorption/desorption( BET),H_2-temperature programmed reduction( H_2-TPR),H_2-chemisorption,O_2 pulse titration and temperature programmed oxidation( TPO) methods. Obtained results exhibited the synthesis solution pH showed a significant influence on the activity and selectivity in partial oxidation of methane reaction. The methane conversion,CO selectivity and H_2 yield were enhanced by increasing of the synthesis solution pH. Compared to other catalysts,the catalyst that synthesized at pH of 13.80,showed a superior ability in syngas production with a H_2/CO ratio of near 2 and also a proper stability against deactivation during the partial oxidation of methane.     

Ni/Al2O3催化甲烷裂解

分别通过浸渍法和共沉淀法制备了不同Ni负载量的Ni/Al2O3催化剂。考察了Ni负载量、制备方法以及反应温度对Ni/Al2O3催化甲烷裂解性能的影响。结果表明,在550℃,浸渍法制备的Ni/Al2O3催化剂,当Ni负载量为20%(质量分数)、Ni金属平均粒径为11.25 nm时,具有最佳的甲烷催化裂解效果,其每摩尔Ni的氢气产量和每克Ni碳产量分别为164 mol和15.30 g。催化剂制备方法对Ni/Al2O3甲烷催化裂解反应有显著影响,相同Ni负载量共沉淀法制备的Ni/Al2O3甲烷催化裂解总体效果要好于浸渍法制备的Ni/Al2O3,而且反应过程中生成的碳纤维较长,管径也较均一。550℃时,共沉淀法制备的Ni负载量为41.2%(质量分数)的Ni/Al2O3催化剂在反应至350 min时,仍保持着30%以上的转化率。