FT-IR Study of Carbon Nanotube Supported Co-Mo Catalysts

In this paper, adsorption properties of dibenzothiophene (DBT) on carbon nanotube, carbonnanotube supported oxide state and sulfide state CoMo catalysts are studied by using thermal gravi-metric analysis (TGA) technique and FT-IR spectroscopy. Activated carbon support, 7-A1203 supportand supported CoMo catalysts are also subjected to studies for comparison. It was found that sulfidestate CoMoS/MWCNT, CoMoS/AC and CoMoS/γ-A12O3 catalysts adsorbed much more DBT moleculesthan their corresponding oxide state catalysts, as well as their corresponding supports. The chemicallyadsorbed DBT aromatic molecules did not undergo decomposition on the surface of supports, supportedoxide state CoMo catalysts and sulfide state CoMo catalysts when out-gassing at 373 K. FT-IR results indicated that DBT molecules mainly stand upright on the active sites (acid sites and/or transition active phases) of CoMoS/MWCNT catalyst. However, DBT aromatic molecules mainly lie flat on MWCNT and CoMoO/MWCNT.     

Study of Carbon Nanotube Supported Co-Mo Selective Hydrodesulphurization Catalysts for Fluid Catalytic Cracking Gasoline

In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization （HDS） of fluid catalytic cracking （FCC） gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene as model compounds to simulate FCC gasoline. The results show that the Co-Mo/CNT has very high HDS activity and HDS/hydrogenation selectivity comparing with the Co-Mo/γ-Al2O3 and Co-Mo/AC catalyst systems. The saturation ratio of cyclohexene was lower than 50%, and the saturation ratio of 1,3-di-isobutylene lower than 60% for the Co-Mo/CNT catalysts. Co/Mo atomic ratio was found to be one of the most important key factors in influencing the hydrogenation selectivity and HDS activity, and the most suitable Co/Mo atomic ratio was 0.4. Co/CNT and Mo/CNT mono-metallic catalysts showed lower HDS activity and selectivity than the Co-Mo/CNT bi-metallic catalysts.     

States of Carbon Nanotube Supported Mo-Based HDS Catalysts

The dispersion of the active phase and loading capacity of the Mo species on carbon nanotube (CNT) was studied by the XRD technique. The reducibility properties of Co-Mo catalysts in the oxide state over CNTs were investigated by TPR, while the sulfided Co-Mo/CNT catalysts were characterized by means of the XRD and LRS techniques. The activity and selectivity with respect to the hydrodesulfurization (HDS) performances on carbon nanotube supported Co-Mo catalysts were evaluated. It was found that the main active molybdenum species in the oxide state MoO3/CNT catalysts were MoO2, but not MoO3, as generally expected. The maximum loading before the formation of the bulk phase was lower than 6% (percent by mass, based on MoO3). TPR studies revealed that the active species in the oxide state Co-Mo/CNT catalysts were reduced more easily at relatively lower temperatures in comparison to those of the Co-Mo/γ-Al2O3 catalysts, indicating that the CNT support promoted or favored the reduction of the active species. The active species of a Co-Mo-0.7/CNT catalyst were more easily reduced than those of the Co-Mo/CNT catalysts with Co/Mo atomic ratios of 0.2, 0.35, and 0.5, respectively, suggesting that the Co/Mo atomic ratio has a great effect on the reducibility of the active species. It was found that the incorporation of cobalt improved the dispersion of the molybdenum species on the support, and a phenomenon of mobilization and re-dispersion had occurred during the sulfurization process, resulting in low valence state Mo3S4 and Co-MoS2.17 active phases. HDS measurements showed that the Co-Mo/CNT catalysts were more active than the Co-Mo/γ-Al2O3 ones for the desulfurization of DBT, and the hydrogenolysis/hydrogenation selectivity of the Co-Mo/CNT catalysts was also much higher than those of the Co-Mo/γ-Al2O3. The Co-Mo/CNT catalyst with a Co/Mo atomic ratio of 0.7 showed the highest activity, whereas the catalyst with a Co/Mo atomic ratio of 0.35 had the highest selectivity.     

Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery

Effects of carbon nanotubes (CNT) and alumina (γ-Al2O3) supports on the catalytic activities of hydrodesulfurization (HDS) process over CoMo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MoO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the r...     

Weakening internal diffusion effect in selective hydrodesulfurization of FCC gasoline by novel designed eggshell CoMoS/Al2O3 catalysts

A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization (HDS) of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.     

碳纳米管负载Co-Mo催化剂在孤岛减压渣油加氢裂化反应中的应用

采用等体积浸渍法制备了一系列不同Co/Mo原子比的碳纳米管（CNT）负载Co Mo催化剂。将该系列催化剂用于孤岛减压渣油加氢裂化反应，评价其催化效果，并在相同反应条件下与 γAl2O3负载Co-Mo催化剂的催化性能进行比较。结果表明，Co-Mo/CNT催化剂的催化效果略低于Co-Mo/γAl2O3催化剂。Co/Mo原子比对Co-Mo/CNT催化剂的催化效果有较大的影响。与相同载体的催化剂相比，当Co/Mo原子比为0.50时，Co-Mo/CNT催化剂具有最佳的催化效果，而Co-Mo/γAl2O3催化剂在Co/Mo原子比为0.35时具有最佳的催化效果。     

XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts

In this paper, the effect of catalytic support and sulfiding method on the chemical state of supported Co-Mo catalysts is studied by XPS. After sulfidation with in-situ method, the majority of molybdenum in CNT supported CoMo catalyst is transferred to a species with a formal chemical state Mo(Ⅳ) in MoS2 phase, and the rest to Mo(Ⅴ) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-. In case of CoMo/γ-Al2O3 catalyst sulfided with in-situ method, a fraction of molybdenum is transferred to formal state Mo(Ⅳ) in the form of MoS2, but there is still a mount of unreduced Mo(VI) phase which is difficult to be sulfided. In CoMo/CNT catalyric system sulfided with ex-situ method, Mo(IV) in the form of MoS2 is detected along with a portion of unreduced Mo(VI) phase, suggesting that not all the Mo phases are reduced and sulfided by ex-situ method. As for CoMo/γ-Al2O3, a portion of molybdenum is sulfided to intermediate reduced state Mo(V) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-, in addition, there is still a fraction of unreduced Mo(Ⅵ)phase. XPS analyses results suggest that CNT support facilitates the reduction and sulfidation of active species to a large extent, and that alumina support strongly interacts with active species, hereby producing a fraction of phase which resists complete sulfiding. Catalytic measurements of catalysts in the HDS of dibenzothiophene (DBT) show that CoMo/CNT catalysts are of higher HDS activity and selectivity than CoMo/γ-Al2O3 catalyst, which is in good relation with the sulfiding behavior of the corresponding catalyst.     

二苯并噻吩在MoO3/γ-Al2O3催化剂上的自发单层分散

二苯并噻吩(DBT)在80 ℃下，保持24 h即可在催化剂表面发生自发单层分散，通过XRD分析测定其分散阈值为0.23 gDBT/g MoO3/γ-Al2O3，大于经计算得出的0.15 g/g的平躺吸附密置单层分散容量，在排除实验误差后，推测DBT在MoO3/γ-Al2O3表面存在通过硫原子的端连吸附，FT-IR分析结果与上述推测相一致，分析认为DBT可能通过硫原子吸附在MoO3/γ-Al2O3表面的酸中心上。     

CO吸附原位红外光谱结合分子模拟计算研究FCC汽油加氢脱硫催化剂的选择性

以脱硫选择性不同的2组催化裂化汽油加氢脱硫催化剂为研究对象, 采用CO吸附原位红外光谱表征了2组催化剂的活性相特征, 并通过分子模拟计算方法比较了助剂Co加入前后噻吩和1-己烯在催化剂表面的电荷分布、吸附能及其加氢反应的活化能等, 探讨了助剂Co的加入对选择性加氢脱硫催化剂脱硫选择性的作用机理. 结果表明, 加氢脱硫催化剂CoMoS活性相的增加有利于提高催化剂的加氢脱硫/加氢降烯烃(HDS/HYD)选择性. 与1-己烯加氢位相比, Co的加入显著提高了噻吩分子加氢位的缺电子性, 噻吩在催化剂表面的吸附度增强, 显著降低噻吩加氢反应的能垒, 从而使噻吩加氢反应更易进行. 这也表明CoMoS为高HDS活性、高HDS/HYD选择性的活性相.     

介孔碳担载的 Co-Mo 和 Ni-Mo 加氢脱硫催化剂

 自制介孔碳 (CMC) 具有比传统活性碳 (AC) 更大的比表面积、孔径和孔体积, 以其为载体, 在浸渍液中加入螯合剂, 采用等量浸渍法制备了 Co-Mo/CMC 和 Ni-Mo/CMC 催化剂, 分别用于模型汽油和柴油加氢脱硫反应. 结果表明, Co-Mo/CMC 和 Ni-Mo/CMC 催化剂具有比 Co-Mo/AC 催化剂更好的织构性质和加氢脱硫活性. 在模型汽油的加氢脱硫反应中, Co-Mo/CMC 催化剂活性比工业催化剂 Co-Mo/Al2O3 高得多; 而在模型柴油的加氢脱硫反应中, Ni-Mo/CMC 催化剂活性也比工业催化剂 FH-98 高得多.     

Synthesis of Ni2P promoted trimetallic NiMoW/γ-Al2O3 catalysts for diesel oil hydrotreatment

The Ni2P promoted and γ-Al2O3 supported NiMoW sulfide catalyst consisting of 4 wt% Mo, 22 wt% W, 2 wt% Ni and 2.5 wt% Ni2P was synthesized by a co-impregnation method. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, NH3 temperature-programmed desorption (NH3-TPD) and transmission electron microscopy (TEM). The results showed that Ni2P, Ni, Mo and W species were highly dispersed over γ-Al2O3. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) showed that the presence of Ni2P brought a strong promotional effect on the HDS activity, which was further confirmed by the HDS and hydrodenitrogenation (HDN) of diesel oil under industrial conditions. The enhancement in HDN activity and stability by Ni2P addition could be attributed more to the effect of new active sites of Ni2P than that of acidity modification. The as-prepared Ni2P-NiMoW/γ-Al2O3 catalyst showed better hydrotreating performance than NiMoW/γ-Al2O3 and commercial catalysts.     

负载型碳氧化钼催化剂的制备及其二苯并噻吩的HDS活性

通过XRD物相分析和利用小型在线质谱仪,对负载的或体相的氧化钼利用正己烷作为碳源,进行程序升温碳化考察,对所制备的负载型催化剂进行了二苯并噻吩（DBT）加氢脱硫（HDS）活性评价。实验发现,与采用甲烷相比,采用正己烷作为碳源进行碳化可以适当降低碳化所需要的温度,但对于HDS反应来说,并不是碳化越完全催化效果越好。对30%MoO3/γ-Al2O3进行碳化时,碳化原料组成为正己烷/氢气＝0.025（摩尔比）,在620℃碳化1ｈ所得催化剂具有比较好的DBT HDS活性。讨论了制备因素对HDS活性的影响。     

载体对负载型Ni-B催化剂催化2-乙基蒽醌加氢制H2O2反应性能的影响

采用还原剂浸渍法将Ni-B非晶态合金负载到SiO2,γ-Al2O3和活性炭(AC)上,以2-乙基蒽醌选择加氧制H2O2为探针反应,系统研究了载体对Ni-B非晶态合金催化剂结构、热稳定性和催化性能的影响.结果表明,将Ni-B负载到载体上后,其晶化温度显著提高,各催化剂热稳定性依次为Ni-B/AC＞Ni-B/SiO2＞Ni...     

压力和温度对4-甲基二苯并噻吩和二苯并噻吩加氢脱硫反应的影响

研究了4-甲基二苯并噻吩(4-MDBT)和二苯并噻吩(DBT)在CoMo/γ-Al2O3上的加氢脱硫反应产物分布及其可能的反应网络,通过反应压力和温度对产物分布影响的研究,揭示了加氢脱硫反应的可能机理。研究发现4-MDBT在CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径和加氢路径进行,且两者反应速率相当；DBT在 CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径进行。4-MDBT分子位于4位的甲基阻碍其在催化剂表面通过硫原子的端连吸附,从而降低了其直接氢解脱硫路径的反应速率,因而也降低了其总的加氢脱硫转化率。反应压力降低,DBT和4-MDBT加氢脱硫反应中加氢路径反应速率明显下降,而其对氢解路径影响较小,但效果却与加氢路径相反,反应压力对4-MDBT转化率的影响大于DBT。反应温度对DBT和4-MDBT加氢脱硫反应中加氢路径和氢解路径都有明显影响,但是对DBT加氢脱硫反应中氢解路径的影响小于加氢路径,而对4-MDBT加氢脱硫反应中氢解路径的影响稍高于加氢路径,4-MDBT分子中甲基的供电子作用有利于相连苯环的加氢反应。     

Simultaneous operation of dibenzothiophene hydrodesulfurization and methanol reforming reactions over Pd promoted alumina based catalysts

In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and tri-metallic(Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism.     

Al2O3性质对加氢脱硫催化剂Co-Mo/Al2O3活性相形成的影响

以两种商用Al2O3为载体,制备了汽油选择性加氢脱硫催化剂Co-Mo/Al2O3,并采用红外光谱、X射线衍射、N2吸附-脱附、透射电镜、扫描透射-能谱和X射线光电子能谱等手段系统研究了载体物化性质对催化剂活性相形成的影响.结果表明,表面羟基数量少和结晶程度高的载体与活性金属间相互作用减弱,促进了Mo物种的硫化还原,使MoS2片晶的尺寸和层数增加,且其硫化态催化剂上CoMoS活性位更多,CoMoS/MoS2比更大,因而显著提高了相应Co-Mo催化剂加氢脱硫活性和选择性.     

The remarkable enhancement of CO-pretreated CuO-Mn2O3/γ-Al2O3 supported catalyst for the reduction of NO with CO: the formation of surface synergetic oxygen vacancy

NO reduction by CO was investigated over CuO/γ-Al2O3, Mn2O3/γ-Al2O3, and CuOMn2O3/γ-Al2O3 model catalysts before and after CO pretreatment at 300 °C. The CO-pretreated CuO-Mn2O3/γ-Al2O3 catalyst exhibited higher catalytic activity than did the other catalysts. Based on X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/Vis diffuse reflectance spectroscopy (DRS), Raman, and H2-temperature-programmed reduction (TPR) results, as well as our previous studies, the possible interaction model between dispersed copper and manganese oxide species as well as γ-Al2O3 surface has been proposed. In this model, Cu and Mn ions occupied the octahedral vacant sites of γ-Al2O3, with the capping oxygen on top of the metal ions to keep the charge conservation. For the fresh CuO/γ-Al2O3 and Mn2O3/γ-Al2O3 catalysts, the -Cu-O-Cu- and -Mn-O-Mn- species were formed on the surface of γ-Al2O3, respectively; but for the fresh CuO-Mn2O3/γ-Al2O3 catalyst, -Cu-O-Mn- species existed on the surface of -Al2O3. After CO pretreatment, -Cu-□-Cu- and -Mn-□-Mn- (□ represents surface oxygen vacancy (SOV)) species would be formed in CO-pretreated CuO/γ-Al2O3 and CO-pretreated Mn2O3/γ-Al2O3 catalysts, respectively; whereas -Cu-□-Mn- species existed in CO-pretreated CuO-Mn2O3/γ-Al2O3. Herein, a new concept, surface synergetic oxygen vacancy (SSOV), which describes the oxygen vacancy formed between the individual Mn and Cu ions, is proposed for CO-pretreated CuO-Mn2O3/γ-Al2O3 catalyst. In addition, the role of SSOV has also been approached by NO temperature-programmed desorption (TPD) and in situ FTIR experiments. The FTIR results of competitive adsorption between NO and CO on all the CO-pretreated CuO/γ-Al2O3, Mn2O3/γ-Al2O3, and CuO-Mn2O3/γ-Al2O3 samples demonstrated that NO molecules mainly were adsorbed on Mn2+ and CO mainly on Cu+ sites. The current study suggests that the properties of the SSOVs in CO-pretreated CuO-Mn2O3/γ-Al2O3 catalyst were significantly different to SOVs formed in CO-pretreated CuO/γ-Al2O3 and Mn2O3/γ-Al2O3 catalysts, and the SSOVs played an important role in NO reduction by CO.     

Composite surfactants aided solvothermal synthesis and catalytic hydrogenation property of oil soluble bimetallic CoMoS nanoparticles

Oil-soluble bimetallic CoMoS nanoparticles were successfully synthesized by a composite-surfactants-aided-solvothermal process. The surface hydrophilicity and functionality of the products were investigated through transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectra, and Ultraviolet (UV) spectra analysis. The catalytic performance of hydrogenation on the CoMoS nanoparticles was studied with naphthalene as a model compound. It was found that CoMoS catalysts supported on active carbon (AC) was more active than conventional MoS2/γ-Al2O3. The activity of CoMoS/AC can be tailored through the change of the Co/(Co+Mo) atomic ratio.     

β-Mo2N0.78/γ-Al2O3催化剂的制备及其噻吩加氢脱硫活性的研究

以γ-Al2O3为载体，钼酸铵为氧化钼前驱体，采用在N2-H2气氛下的程序升温还原氮化反应，制备β-Mo2N0.78/γ-Al2O3催化剂，以噻吩为模型化合物，考察了该催化剂的加氢脱硫反应性能，以及反应温度、氢还原预处理和钴、镍助剂的引入等因素对催化剂活性的影响。结果表明，在320 ℃～400 ℃之间，随着反应温度的升高，催化剂的活性逐渐增加；预还原则降低了催化剂的活性；添加钴、镍均在一定负载量范围内可以改善β-Mo2N0.78/γ-Al2O3催化剂的加氢脱硫活性，但镍对催化剂活性的影响要小于钴。     

镍钼杂多酸制备NiMo/γ-Al2O3催化剂及硼、钴或镍改性氧化铝的影响（英文）

A hydrotreating NiMo/γ-Al2O3 catalyst(12 wt% Mo and 1.1 wt% Ni) was prepared by impregnation of the support with the Anderson-type heteropolyoxomolybdate(NH4)4Ni(OH)6Mo6O18.Before impregnation of the support,it was modified with an aqueous solution of H3BO3,Co(NO3)2,or Ni(NO3)2.The catalysts were investigated using N2 adsorption,O2 chemisorption,X-ray diffraction,UV-Vis spectroscopy,Fourier transform infrared spectroscopy,temperature-programmed reduction,temperature-programmed desorption,and X-ray photoelectron spectroscopy.The addition of Co,Ni,or B influenced the Al2O3 phase composition and gave increased catalytic activity for 1-benzothiophene hydrodesulfurization(HDS).X-ray photoelectron spectroscopy confirmed that the prior loading of Ni,Co or B increased the degree of sulfidation of the NiMo/γ-Al2O3 catalysts.The highest HDS activity was observed with the NiMo/γ-Al2O3 catalyst with prior loaded Ni.