Dibenzothiophene Hydrodesulfurization Activity of MoS2 Supported in Sol–Gel ZrO2–TiO2 Mixed Oxides

Abstract

In this work, we report the effect of support composition on the properties of MoS₂ impregnated in sol–gel ZrO₂–TiO₂ mixed oxides as dibenzothiophene hydrodesulfurization catalyst. The supports calcined at 500°C were characterized by N₂ physisorption and X-ray diffraction (electronic radial distribution function). The oxidic impregnated materials (2.8 Mo atoms/nm²) were sulfided at 400°C under a H₂S/H₂ stream. The sample impregnated on the equimolar support showed the highest activity per mass of catalysts whereas the one with TiO₂ carrier was superior in a per mass of Mo basis. Marked differences in products selectivity were observed by TiO₂ addition in the supports. The hydrodesulfurization route to partially hydrogenated compounds was favored over the mixed oxides-supported catalysts meanwhile the direct desulfurization (to biphenyl) was promoted on the ZrO₂-supported solid. It is suggested that among other properties the dispersion and morphology of the MoS₂ phase could influence that behavior.     

Co-Ru/γ-Al2O3 Catalyst Modified With ZrO2 for Fischer-Tropsch Synthesis

Abstract

Using an incipient impregnation method, a Co-Ru bimetallic catalyst was prepared. The effects of the ZrO₂ modification of support on heavy hydrocarbon synthesis were investigated in a fixed-bed reactor. The results indicated that the ZrO₂ modification could block defects of γ-Al₂O₃ crystal lattice, weaken the interaction between support and Co, and hinder or prevent the formation of cobalt aluminate. Zr reacted with Co to form the Co-Zr species, which is easily reduced under lower temperature. It caused an increase in the amount of easily reducible Co species and a decrease in the amount of uneasily reducible Co species. Then the reduction extent of cobalt-based catalyst was raised under the typical reduction condition. Meanwhile, support of γ-Al₂O₃ was modified with ZrO₂, and the interface of Co-ZrO₂ formed. The Co-ZrO₂ interface led to an increase of the intensity of the bridge-form CO adsorption, which CO facilitates to be dissociated. At H₂/CO molar ratio in feed 2.0, 503 K, 1.5 MPa, and 800 hr^?1, the catalyst exhibited better catalytic performance. The CO conversion was 93.27%, the C₅ ⁺ selectivity was 82.56%, and the chain growth factor was 0.81.     

Pt/ZrO2- Al2O3 催化剂芳构化反应性能研究

在微型反应装置上考察以ZrO2和γ-Al2O3为载体负载Pt的单金属催化剂和多金属催化剂的反应活性、选择性、稳定性. 实验结果表明，以ZrO2和γ-Al2O3为载体负载Pt的单金属催化剂ZAP具有非常好的正庚烷转化活性和甲苯选择性，而裂化性能较弱，反应初期正庚烷转化率为87.5%，甲苯收率达到33.0%，C3+C4收率在10.5%左右，但积炭速率较快，催化剂的稳定性略差；ZrO2和γ-Al2O3复合载体和单纯γ-Al2O3载体的酸性相当，在Pt/ZrO2-γ-Al2O3体系中引入La，抑制了催化剂的脱氢环化活性和加氢裂化性能，随着催化剂中La含量的增加，这种抑制作用更加明显。Sn的引入增强了催化剂的酸性，在高温高压下反应，含0.1%Sn的催化剂的裂化活性提高，而较高含量的Sn（0.3%）的加入明显降低了催化剂的反应活性和选择性。     

Direct conversion of natural gas into COx-free hydrogen and MWCNTs over commercial Ni–Mo/Al2O3 catalyst: Effect of reaction parameters

A commercial hydrotreating nickel molybdate/alumina catalyst was used for the direct conversion of natural gas (NG) into CO_x-free hydrogen and a co-valuable product of multi-walled carbon nanotubes (MWCNTs). The catalytic runs were carried out atmospherically in a fixed-bed flow reactor. The effect of reaction temperature between 600 and 800 °C, and dilution of the NG feed with nitrogen as well as pretreatment of the catalyst with hydrogen were investigated. At a reaction temperature of 700 °C and dilution ratio of NG/N₂ = 20/30, the optimum yield of H₂ (～80%) was obtained with higher longevity. However, using the feed ratio of NG/N₂ = 30/20, the optimum yield of MWCNTs was obtained (669%). X-ray diffraction pattern for the catalyst after the reaction showed that the MWCNTs were grown on the catalyst at all reaction temperatures under study. TEM pictures revealed that the as-grown MWCNTs at 600, 650 and 800 °C are short and long with a low graphitization degree. At 700 °C a forest of condensed CNTs is formed, whereas both carbon nanofibers and CNTs were formed at 750 °C.     

Recovery of precious metals from spent Mo–Co–Ni/Al2O3 catalyst in organic acid medium: Process optimization and kinetic studies

In present study, the leaching kinetics of the spent Mo–Co–Ni/Al₂O₃ catalyst was investigated in the presence of formic acid as an organic leaching agent. Firstly, the spent catalyst was roasted in different roasting temperature (200–700?°C) and time (15–240?min), the maximum metal extraction was achieved that at 500?°C with 90?min. Then, the leaching experiments were carried out to determine the influences of process parameters following; particle size, liquid/solid ratio, formic acid concentration, leaching temperature, leaching time and stirring speed. According to the experimental results, the highest dissolution rates of molybdenum (Mo, 75.82%), cobalt (Co, 96.81%), nickel (Ni, 93.44%) and aluminum (Al, 19.46%) were reached under optimum experimental conditions; particle size +75???30?µm; liquid/solid ratio 10?ml/g; formic acid concentration 0.6?M; leaching temperature 80?°C; leaching time 90?min and stirring speed 300 r/min. Moreover, the leaching kinetics clearly reveal that the leaching reaction is controlled by liquid film diffusion and that the activation energy values (E_a) of Co, Ni, Mo and Al were to be 24.49, 25.98, 32.36 and 33.47?kJ/mol, respectively. In conclusion, the leaching process can be conducted in the presence of formic acid for the various industrial wastes in similar structure and composition to Mo–Co–Ni/Al₂O₃ spent catalyst.     

Al2O3和Cr2O3陶瓷涂层耐蚀性的研究

报道对Al2O3和Cr2O3两种金属氧化陶瓷涂层材料进行的耐蚀性试验研究,该项研究结果表明,Cr2O3涂层具有优异的耐蚀性,而Al2O3涂层具有较好的耐盐、碱腐蚀性。     

焙烧温度对Al2O3载体及Pd／Al2O3催化剂性能的影响

采用CO2气体成胶制备了Al2O3载体,考察了载体焙烧温度对载体和相应Pd／Al2O3催化剂物理化学性质及催化性能的影响,并采用X射线衍射、BET等技术对载体及催化剂性能进行了表征。结果表明,随焙烧温度的升高,载体的比表面积、孔容减小,平均孔径逐渐增大,孔分布较集中。所制得的拟薄水铝石较纯净。400—800℃焙烧时,Al2O3载体只有γ—Al2O3晶型;1050℃时,主要以θ-Al2O3为主;到1250℃已完全转变为α—Al2O3。Pd／Al2O3催化剂均具有较高的双烯加氢活性和选择性,其中以970℃和1050℃焙烧载体制备的催化剂为最优。     

Production of Lubricating Base Oil Using a Moist SiO2/γ-Al2 O3 Catalyst

Abstract

The catalyst SiO₂/γ-Al₂ O₃ treated by micro-wetness air to produce lubricating base oil was studied in this article. The satisfactory reaction temperature, the treatment temperature, and the proper content of active composition was researched. Under the best reaction conditions with a reaction temperature of 170°C, a reaction pressure at 6.0 Mpa, the volume velocity at 0.5 h^?1. The polymerization of α-olefin was performed at a microreactor and produced lubricating base oil with the kinetic viscosity at 38.19 mm² · s^?1, the bromine number at 5.78 g(Br) · (100 g)^?1, and the pour point at ?43.0°C. Then the structure of the catalyst was determined by Brunauer, Emmett and Teller (BET) technology. The result shows that when the optimal micro-wetness air was 45°C, the reaction temperature was 800°C, and the amount of active composition was 12%, and the catalyst has high catalytic activity and wide market prospect.     

Influence of Additives on Hydrodesulfurization Activity of Fe-Mo/Al2O3 Catalysts

Based on the study relating to the influence of additives on the hydrodesulfurization performance of Fe-Mo-Al2O3 catalysts, it was found out that the introduction of additives could increase considerably the activity of Fe-Mo/Al2O3 catalysts in the reaction of hydrodesulfurization of gasoline and diesel fractions. The introduction of zeolites （HY, HZSM） and other additives could lead to an increase of the concentration of acid centers, which were able to react with sulfur compounds, along with an increase of total catalysts＇ pore volume, which could improve the capability of catalyst to adsorb the hydrogen and feed oil.     

Modeling of Coke Formation and Catalyst Deactivation in Propane Dehydrogenation Over a Commercial Pt-Sn/γ-Al2O3 Catalyst

Propane dehydrogenation was carried over a commercial Pt-Sn/γ-Al₂O₃ catalyst at atmospheric pressure and reaction temperatures of 580, 600, and 620°C and WHSV of 11 h^?1 in an experimental tubular quartz reactor. Propane conversions were measured for catalyst time on stream of up to nine days. The amounts of coke deposited on the catalyst were measured after one, three, six, and nine days on stream using a thermogravimetric differential thermal analyzer (TG-DTA) for each reaction temperature. The coke formation kinetics was successfully described by a coke formation model based on a monolayer-multilayer mechanism. In addition, catalyst deactivation was presented by a time-dependant deactivation function. The kinetic order for monolayer coke formation was found to be two, which would support a coke formation step involving two active sites. The kinetic order for multilayer coke formation was found to be zero. The activation energy for monolayer coke formation was found to be 29.1 kJ/mol, which was lower than the activation energy of about 265.1 kJ/mol for multilayer coke formation indicating that the presence of metals can promote coke formation on the catalyst surface.     

Effects of Impregnation Solvents on Catalytic Performance of Co-Ru-ZrO2/γ-Al2O3 Catalyst for Fischer-Tropsch Synthesis

Abstract

Used ZrO₂ modified γ-Al₂O₃ as support, Co-Ru catalysts were prepared by incipient impregnation method. The effects of impregnation solvents on the performances of catalysts were examined. The catalyst was prepared with ethanol solution and high Co dispersion was obtained, exhibiting highest activity of CO hydrogenation, very low methane selectivity, and high heavy hydrocarbon C₅ ⁺ selectivity. The catalysts were prepared with aqueous solution and methanol solution, and the reaction behaviors were similar. The solvent isopropanol caused the lowest catalytic activity and highest methane selectivity. Increasing the reaction temperature enhanced the CO hydrogenation rate, and the CO conversion slightly increased the CO₂ selectivity and favored the formation methane and light hydrocarbons, while the chain growth probability decreased. For the catalyst prepared with ethanol, the CO conversion, the CH₄ selectivity, and the C₅ ⁺ selectivity were 94.16%, 5.65%, and 88.2%, respectively, and the chain growth probability was 0.87 at 493 K, 1.5 MPa, 800 h^?1, and n(H₂):n(CO) = 2.0 in feed.     

Study on flame propagation of premixed N2O–NH3/N2O–NH3–C3H8 in cylindrical vessels

The flame propagation behavior of premixed N₂O–NH₃/N₂O–NH₃–C₃H₈ was experimentally investigated in elongated vented cylindrical vessels with central ignition. The effect of vessel diameter and propane concentration ([C₃H₈] = 1.96–7.41 wt.%) on the process of flame acceleration was studied and discussed. The results revealed that the maximum value of flame acceleration rate was found in the cylindrical vessel with an inner diameter of 7 mm, followed by 5 mm, 10 mm, and 15 mm. At a constant vessel diameter, the rate of flame acceleration was noticeably improved by adding propane ([C₃H₈] = 1.96–3.85 wt.%) to the premixed N₂O–NH₃. However, a further increase in the propane fraction up to 5.66%, caused a decline in the flame acceleration rate, probably as a consequence of a combined effect between the reduction of oxygen and greater dilution of the ammonia in the total concentration.     

CoMo/ZrO2-Al2O3催化剂的加氢脱硫活性

制备了CoMo／ZrO2-Al2O3系列催化剂，用程序升温还原技术考察了ZrO2对催化剂还原性的影响，发现ZrO2的质量分数为12％时，ZrO2与活性组分间存在较强的相互作用。以二苯并噻吩为探针化合物，考察了催化剂在不同温度下的加氢脱硫(HDS)活性。结果表明，以ZrO2含量为12%的复合氧化物为载体，负载4％CoO和15％MoO3的催化剂具有最佳的催化活性，优于广泛使用的进口工业HDS催化剂KF707。     

Al2O3 PLOT毛细管气相色谱分析C2组分

参考新的国家标准《工业用乙烯中烃类杂质的测定-气相色谱法》中的分析方法，使用Al2O3PLOT毛细管色谱柱分析C2组分。找出了最优化的色谱柱温操作条件：初始温度103℃，保持时间0min：一阶降温速率20℃／min，一阶保持温度55℃，保持时间2min；二阶升温速率15℃／min，终止温度140℃，保持时间3min。此法的准确性、重复性和稳定性均良好，适合于乙烯生产的中间控制分析。     

Study of the productivity of MWCNT over Fe and Fe–Co catalysts supported on SiO2, Al2O3 and MgO

In the present study, multi-walled carbon nanotubes (MWCNT) were prepared in good quality and quantity, MWCNT were produced using the catalytic chemical vapor deposition (CCVD) technique and the carbon source was acetylene. Different catalysts were synthesized based on iron and a mixture of iron and cobalt metal supported on SiO₂, Al₂O₃ or MgO. The effect of parameters such as iron concentration, support type, bimetallic catalyst and the method of catalyst preparation has been investigated in the production of MWCNT. The quality of as-made nanotubes was investigated by the high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis (TGA). The best yield of MWCNT was 30 times of the amount of the used catalyst. The high yield of MWCNT was gained by 40 wt.% Fe on alumina support which was prepared by the sol–gel method. TEM analysis was done for the carbon deposit, which revealed that the walls of the MWCNT were graphitized, with regular inner channel and uniform diameter. It reflected a reasonable degree of purity. The TGA showed that MWCNT was decomposed at 635 °C by a small rate indicating a high thermal stability and well crystalline formation of the produced MWCNT.