Nitrocyclohexane hydrogenation to cyclohexanone oxime over mesoporous carbon supported Pd catalyst

Mesoporous carbon materials (MC) were prepared by soft template, hard template and hydrothermal synthesis methods. And mesoporous carbon supported palladium catalysts were obtained from incipient impregnation method. The prepared samples were characterized by nitrogen adsorption–desorption, X-ray diffraction, transmission electron microscopy and hydrogen chemisorption. Palladium supported on mesoporous carbon prepared by hard template method shows better catalytic performance, it gives the 82.2% selectivity to cyclohexanone oxime at the nitrocyclohexane conversion of 99.4% under the mild reaction conditions of 0.5 MPa and 323 K.     

Reactivity of olefins in the hydrodesulfurization of FCC gasoline over CoMo sulfide catalyst

To achieve selective hydrodesulfurization (HDS) of fluid catalytic-cracked (FCC) gasoline for producing sulfur-free gasoline (S < 10 ppm), the reactivity of various olefins contained in FCC gasoline on CoMoP/Al₂O₃ sulfide catalysts was investigated. Isomerization of the CC double bond from the terminal position to an internal position was observed. The steric hindrance around the CC double bond suppresses the reactivity of olefin hydrogenation. The sulfidation temperature of the catalyst has a major influence on olefin hydrogenation active sites. Addition of the appropriate amount of cobalt (Co/Mo ratio approximately 0.6) contributes to the suppression of olefin hydrogenation at high reaction temperature (260 °C). From the comparison of catalytic performance and characterization of our CoMoP/Al₂O₃ catalyst with an analogous commercial catalyst, it is suggested that the hydrogenation of olefins depends not only on the state of the Mo CUS but also on the steric effects of both olefin structure and MoS₂ crystalline structure.     

Recycling of waste lubricant oil into chemical feedstock or fuel oil over supported iron oxide catalysts

The recycling of waste lubricant oil from automobile industry was found to be best alternative to incineration. Silica (SiO₂), alumina (Al₂O₃), silica-alumina (SiO₂-Al₂O₃) supported iron oxide (10 wt% Fe) catalysts were prepared by wet impregnation method and used for the desulphurisation of waste lubricant oil into fuel oil. The extent of sulphur removal increases in the sequence of Fe/SiO₂-Al₂O₃<Fe/Al₂O₃<Fe/SiO₂ and this might be due to the presence of smaller crystalline size (7.4 nm) of Fe₂O₃ in Fe/SiO₂ catalyst. X-ray diffraction results suggest the presence of iron sulphide in the used catalyst. Gas chromatography with thermal conductivity detector analysis confirms the presence of H₂S in gaseous products. In addition, Fe/SiO₂ catalyst facilitated the formation of lower hydrocarbons by cracking higher hydrocarbons (≈C₄₀) present in waste lubricant oil.     

PtCo supported on ordered mesoporous carbon as an electrode catalyst for methanol oxidation

A catalyst for methanol oxidation, PtCo supported on graphitized mesoporous carbon, has been synthesized and its electrochemical activity for methanol oxidation has been investigated. The graphitized mesoporous carbon support with ordered pore structure and high surface area of 585 m² g⁻¹ was prepared by one-step melt casting method using Al doped hexagonal mesoporous silica as hard templates and mineral pitches as carbon precursors followed by carbonization at 800 °C. The materials were characterized by X-ray diffraction, Raman spectra, field emission scanning electron microscopy, transmission electron microscopy and nitrogen sorption techniques. Cyclic voltammetry and amperometric i-t tests were adopted to characterize the electro-catalytic activities of the materials for methanol oxidation. The results show that the graphitized mesoporous carbon exhibits large electrochemical capacitance and good electric property. After supported with 20 wt%Pt or 20 wt%PtCo nanoparticles, the resultant mesostructured composites show 26-97% higher electrochemical catalytic activity for methanol oxidation than commercial catalyst 20 wt%Pt/C in mass activity (mA mg Pt⁻¹).     

Thermo-catalytic decomposition of waste lubricating oil over carbon catalyst

The thermo-catalytic decomposition of waste lubricating oil over a carbon catalyst was investigated in an I.D. of 14.5mm and length of 640mm quartz tube reactor. The carbon catalysts were activated carbon and rubber grade carbon blacks. The decomposition products of waste lubricating oil were hydrogen, methane, and ethylene in a gas phase, carbon in a solid phase and naphthalene in a liquid phase occurring within the temperature ranges of 700 °C-850 °C. The thermo-catalytic decomposition showed higher hydrogen yield and lower methane yield than that of a non-catalytic decomposition. The carbon black catalyst showed higher hydrogen yield than the activated carbon catalyst and maintained constant catalytic activity for hydrogen production, while activated carbon catalyst showed a deactivation in catalytic activity for hydrogen production. As the operating temperature increased from 700 °C to 800 °C, the hydrogen yield increased and was particularly higher with carbon black catalyst than activated carbon. As a result, carbon black catalyst was found to be an effective catalyst for the decomposition of waste lubricating oil into valuable chemicals such as hydrogen and methane.     

Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron-nickel catalyst supported on alumina

Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over 40Fe:60Al₂O₃, 40Ni:60Al₂O₃ and 20Fe:20Ni:60Al₂O₃ catalysts. High density CNTs of 20 nm diameter were grown over the 20Fe:20Ni:60Al₂O₃ catalyst, whereas low growth density CNTs of 40 and 50 nm diameter were found over 40Fe:60Al₂O₃ and 40Ni:60Al₂O₃ catalysts. Smaller catalyst particles enabled the synthesis of highly dense, long and narrow-diameter CNTs. It was found that a homogeneous dispersion of the catalyst was an essential factor in achieving high growth density. The carbon yield and the quality of CNTs increased with increasing temperature. For the 20Fe:20Ni:60Al₂O₃ catalyst, the carbon yield reached 121% after 90 min at 700 °C. The CNTs were grown according to the tip growth mode. Based on reports regarding hydrocarbon adsorption and decomposition over different faces of Ni and Fe, the growth mechanism of CNTs over the 20Fe:20Ni:60Al₂O₃ catalyst are discussed.     

The reduction of dissolved oxygen by hydrazine over platinum catalyst supported on disordered mesoporous materials

Catalytic reduction of dissolved oxygen by hydrazine at room temperature was investigated on Pt catalysts supported on KTT-1 mesoporous material and Y and ZSM-5 zeolites. Pt catalyst supported on A1KIT-1 mesoporous material exhibited high performance ascribed to the high dispersion of Pt and the large diameter lowering diffusion restriction.     

Hydrogenolysis of sorbitol to glycols over carbon nanofiber supported ruthenium catalyst

Sorbitol hydrogenolysis was carried out over a carbon nanofiber supported ruthenium catalyst prepared by incipient wetness impregnation. The carbon nanofiber supported ruthenium catalyst was shown to have an attracting behavior when compared with a commercial activated carbon supported ruthenium catalyst, especially in terms of selectivity to glycols. The preferable hydrogen partial pressure for sorbitol hydrogenolysis was ca. 8.0 MPa, lower than that usually reported in previous works. Slightly soluble calcium hydroxide, which was used as a basic promoter, remarkably increased the selectivity to glycols, as compared with the soluble sodium hydroxide. The variation of product selectivity with catalyst amount indicated that glycerol was the initial C3 polyol product while propylene glycol was derived from glycerol. The parametric investigation was further focused on the intrinsic features of sorbitol hydrogenolysis.     

IR study of the secondary reaction of ethylene oxide over silver catalyst supported on mesoporous material

The secondary reaction of ethylene oxide over silver catalyst supported on MCM-41 mesoporous material was investigated by thein-situ IR method. MCM-41 mesoporous material with a large content of hydroxyl group was very active in catalyzing the isomerization of ethylene oxide to acetaldehyde. The reduction of hydroxyl group by silane treatment or silver loading suppressed the isomerization of ethylene oxide. The selectivity for ethylene oxide in the partial oxidation of ethylene is enhanced by silane modification, revealing the acceleration of the consumption of ethylene oxide on the hydroxyl group.     

Transformation of cyclopentanone into cyclopentanethiol over a sulfided CoMo/Al2O3 catalyst

The transformation of cyclopentanone in the presence of H₂S/H₂ was investigated at atmospheric pressure over a sulfided CoMo/Al₂O₃ catalyst. The main reaction products were cyclopentanethiol and cyclopentene, the relative amounts of which depended on the reaction temperature and on the H₂S to cyclopentanone molar ratio. The best results were obtained at 220°C, with a 2.5 H₂S to cyclopentanone molar ratio: under these conditions, the cyclopentanethiol molar selectivity remained at about 90%, in a range of cyclopentanone conversion of 10–70%.     

Preparation of Pt/C cathode catalyst supported on chestnut-like mesoporous carbon for fuel cell applications

Fuel cells have received worldwide attention as a next-generation renewable energy technology. However, catalyst cost and durability are the main issue hampering the commercialization of fuel cells. Many studies have focused on the physicochemical properties of the carbon support to improve the catalyst’s properties. Mesoporous carbons are suitable candidates because of their appropriate structural characteristics, including high surface area, large pore size, and regularly interconnected mesopores that permit efficient diffusion of the reactants and by-products. In this study, supports made from chestnut-like carbon consisting of platelet carbon nanofibers were fabricated by selective catalytic gasification of activated carbon. Pt/C catalysts were synthesized from these support structures using the impregnation method. Catalyst performance and characteristics were investigated by N₂ adsorption/desorption isotherms, X-ray diffractions, and the rotating disk electrode technique for the oxygen reduction reaction.     

Hydrogenation of phenol in scCO2 over carbon nanofiber supported Rh catalyst

A catalyst of Rh nanoparticles supported on a carbon nanofiber, 5 wt.% Rh/CNF, with an average size of 2–3 nm has been prepared by a method of incipient wetness impregnation. The catalyst presented a high activity in the ring hydrogenation of phenol in a medium of supercritical CO₂ (scCO₂) at a low temperature of 323 K. The presence of compressed CO₂ retards hydrogenation of cyclohexanone to cyclohexanol under the reaction conditions used, and this is beneficial for the formation of cyclohexanone, increasing the selectivity to cyclohexanone. But the selectivity to cyclohexanone is very low at the completion of reaction in the absence of CO₂, at low CO₂ pressures, and in the presence of pressurized N₂ instead of CO₂. That is, high selectivity to cyclohexanone can be achieved with CO₂ species at higher pressures but not with the application of an inert hydrostatic pressure on the liquid substrate phase.     

Preparation and characterization of mesoporous activated carbon from waste tires

Activated carbons were produced from waste tires and their characteristics were investigated. Rubber separated from waste tires was first carbonized at 500 °C in N₂ atmosphere. Next, the obtained chars were activated with steam at 850 °C. As a result, fairly mesoporous activated carbons with mesopore volumes and BET surface areas up to 1.09 cm³/g and 737 m²/g, respectively, were obtained. To further improve the porous properties of the activated carbons, the char was treated with 1 M HCl at room temperature for 1 day prior to steam activation. This treatment increased mesopore volumes and BET surface areas of the activated carbons up to 1.62 cm³/g and 1119 m²/g, respectively. Furthermore, adsorption characteristics of phenol and a dye, Black 5, on the activated carbon prepared via acid treatment were compared with those of a commercial activated carbon in the liquid phase. Although the prepared carbon had a larger micropore volume than the commercial carbon, it showed a slightly lower phenol adsorption capacity. On the other hand, the prepared carbon showed an obviously larger dye adsorption capacity than the commercial carbon, because of its larger mesopore volume.     

活性炭负载铁催化剂催化羟基化甲苯制备甲酚研究

以活性炭、十二烷基磺酸铁为原料制备了活性炭负载铁催化剂,采用H_2O_2作为羟基化试剂,进行了催化羟基化甲苯制备甲酚的研究。考察了溶剂种类、催化剂用量、反应时间、反应温度及原料摩尔比对甲苯转化率和甲酚选择性的影响,试验结果表明:在溶剂为乙腈,催化剂用量为0.5 g,反应温度为30℃,甲苯与H_2O_2摩尔比为1∶5,反应时间为4 h条件下,羟基化反应后甲苯转化率为28.96%,甲酚选择性81.25%。同时结合甲苯羟基化的反应过程探讨了羟基化反应机理,为甲酚绿色催化合成工艺放大研究提供技术支撑。     

活性炭负载磷钨酸催化合成丁酮1,2-丙二醇缩酮

以活性炭负载磷钨酸为催化剂,丁酮与1,2-丙二醇为原料催化合成丁酮1,2-丙二醇缩酮。研究了丁酮与1,2-丙二醇量比、催化剂用量及反应时间等反应条件对收率的影响。结果表明,在丁酮与1,2-丙二醇的量比为1∶1.5,催化剂的用量占反应物料总质量的1.0%,反应时间为1h的条件下,丁酮1,2-丙二醇缩酮的收率可达81.8%。     

Effect of steam and carbon dioxide pretreatments on methane decomposition and carbon gasification over doped-ceria supported nickel catalyst

Effects of steam (H₂O) and carbon dioxide (CO₂) pretreatments on methane (CH₄) decomposition and carbon gasification over doped-ceria supported nickel catalysts have been studied from 400 to 500 °C. The doped ceria employed were gadolinia-doped ceria and samaria-doped ceria. Results indicate that a drastic increase of both H₂O and CO₂ dissociation activities occurs as the temperature increases from 450 to 500 °C. The formation of the surface hydroxyl species during H₂O treatment inhibits the followed CH₄ decomposition. CO but no CO₂ was formed during CH₄ reaction after H₂O treatment. Carbon deposition during CH₄ decomposition is quite large but can be removed via gasification with afterward CO₂ treatment. However, some of the deposited carbon species is in a form which can not be removed with CO₂ treatment but can be removed with O₂ treatment. And, higher values of the oxygen-ion conductivity and the density of the surface oxygen vacancies lead to higher activities for all dissociation and decomposition reactions.     

Hydrodeoxygenation of dibenzofuran over noble metal supported on mesoporous zeolite

Hydrodeoxygenation has been considered to be one of the most promising methods for bio-oil upgrading. In this paper, the catalytic performance of noble metal supported on mesoporous zeolite in model bio-oil compound hydrodeoxygenation was examined. Dibenzofuran was chosen here because of its refractory nature and large molecular size. Our results indicate that Pt supported on mesoporous ZSM-5 show better performance in dibenzofuran hydrodeoxygenation than Pt/ZSM-5 and Pt/Al₂O₃. The excellent catalytic performance is attributed to the combination of strong acidity and mesopore structure in mesoporous zeolite.     

Low cost growth route for single-walled carbon nanotubes from decomposition of acetylene over magnesia supported Fe-Mo catalyst

A large amount of single wall carbon nanotubes (SWNTs) was successfully produced by thermal decomposition of C₂H, at 800 °C over magnesia supported Fe-Mo bimetallic catalysts in a tubular flow reactor under an atmosphere of hydrogen flow. The growth density of SWNTs increased with increasing the weight percent of the catalyst metals (wt% ratio of two metals: 50 : 50) supported on magnesia (MgO) from 5 to 30 wt%. The yield of SWNTs reached 144.3% over 30 wt% metal-loaded catalyst. Raman measurements showed the growth of bundle type SWNTs with diameters ranging from 0.81 to 1.96 nm. The growth of SWNTs was also identified by thermal gravimetric analysis (TGA) and Raman spectroscopy.     

HF/USY催化剂催化十六碳烯与苯烷基化的研究

采用负载氢氟酸的USY分子筛作为催化剂,对苯和十六碳烯烷基化反应合成十六烷基苯进行了实验研究。使用微型固定床反应器,在反应压力2.5 MPa,苯烯摩尔比10∶1的条件下考察了催化剂组成、反应温度、空速对催化剂性能的影响以及催化剂的稳定性和再生性。研究结果表明,在氟的负载质量分数为3.0%、130℃、空速为3.0 h-1时,十六碳烯的转化率为99.15%,十六烷基苯的选择性为97.03%。HF/USY催化剂具有较好的催化活性和稳定性。     

Biodiesel production from waste cooking palm oil using calcium oxide supported on activated carbon as catalyst in a fixed bed reactor

A reactor has been developed to produce high quality fatty acid methyl esters (FAME) from waste cooking palm oil (WCO). Continuous transesterification of free fatty acids (FFA) from acidified oil with methanol was carried out using a calcium oxide supported on activated carbon (CaO/AC) as a heterogeneous solid-base catalyst. CaO/AC was prepared according to the conventional incipient-wetness impregnation of aqueous solutions of calcium nitrate (Ca(NO₃)₂·4H₂O) precursors on an activated carbon support from palm shell in a fixed bed reactor with an external diameter of 60 mm and a height of 345 mm. Methanol/oil molar ratio, feed flow rate, catalyst bed height and reaction temperature were evaluated to obtain optimum reaction conditions. The results showed that the FFA conversion increased with increases in alcohol/oil molar ratio, catalyst bed height and temperature, whereas decreased with flow rate and initial water content in feedstock increase. The yield of FAME achieved 94% at the reaction temperature 60 °C, methanol/oil molar ratio of 25: 1 and residence time of 8 h. The physical and chemical properties of the produced methyl ester were determined and compared with the standard specifications. The characteristics of the product under the optimum condition were within the ASTM standard. High quality waste cooking palm oil methyl ester was produced by combination of heterogeneous alkali transesterification and separation processes in a fixed bed reactor. In sum, activated carbon shows potential for transesterification of FFA.