Overview of support effects in hydrotreating catalysts

The commercial hydrotreating catalysts are usually composed of a sulfide active phase supported on alumina. It has been known for more than 15 years that other supports might lead to enhanced catalytic properties. The present article summarizes the progress which have been made in this area, often related to new methods of preparation of supports, active phases deposition or activation procedures. The properties of active phases supported on oxides, pure or mixed, basic and acidic supports, zeolites, mesoporous materials, carbon and clays are examined.     

Hydrodesulfurization of thiophene, dibenzothiophene and gas oil on various Co---Mo/TiO2-Al2O3 catalysts

Evaluation of Co---Mo catalysts prepared on various TiO₂-Al₂O₃ supports has been made for thiophene under atmospheric pressure, dibenzothiophene under high pressure and gasoil in a classical pilot plant. Comparison of activities indicates DBT as more representative of a real feedstock and the Co---Mo/TiO₂ (50%)-Al₂O₃ (50%) catalyst appears more active than the Co---Mo/Al₂O₃ sample toward HDS, HDN and hydrodearomatization.     

Alternate use of heavy hydrotreatment and visbreaker naphthas by incorporation into diesel

In order to provide a solution for refineries having limited catalytic reforming capacity, a process scheme for incorporating most of the low octane heavy hydrotreatment and visbreaker naphthas into diesel is presented in this paper. This scheme involves blending the visbreaker naphtha with the feed to the diesel hydrotreatment units, processing this blend at the usual conditions for diesel hydrodesulfurization and changing the cut point in the diesel stabilizer.     

Niobium sulfide as a dopant for Mo/TiO2 catalysts

Mo/TiO₂ catalysts were modified with Nb by two different methods, sol–gel and surface deposition, in order to study the effect of Nb incorporation on the thiophene HDS activity. The results show that the formation of Nb–Ti mixed oxides leads to catalysts with poor HDS activity while the deposition of Nb oxide species on the surface of TiO₂ leads to catalysts with activities larger than those of Mo/Al₂O₃ and Mo/TiO₂. This increase in activity was attributed to the formation of a larger population of Mo sulfur anionic vacancies when Nb was surface deposited on the TiO₂.     

Hartree–Fock periodic study of the chemisorption of small molecules on TiO2 and MgO surfaces

We present ab initio periodic Hartree–Fock calculations (CRYSTAL program) of the adsorption of small molecules on TiO₂ and MgO. These may be molecular or dissociative, depending on the acidic and basic properties of the molecules in gas phase and of the nature of the surface oxide. For the molecular adsorption, the molecules are adsorbed as bases on Ti(+IV) sites, the adsorption energies correlate with the proton affinities. The dissociations on the surface correlate with the gas phase cleavages of the molecule; they also depend on the surface oxide; the oxygen atom of MgO, in spite of its large charge, is poorly reactive and dissociation on MgO is not favorable.

The surface hydrosyl of MgO are more basic than the O of the lattice and water is not dissociated under adsorption. As experimentally observed, NH₃ adsorbs preferentially on TiO₂ and CO₂ on MgO. However, this difference of reactivity should not be expressed in terms of acid vs basic behavior, but in terms of hard and soft acidity. MgO surface is a “soft” acidic surface that reacts preferentially with the soft base, CO₂.

Another important factor is the adsorbate–adsorbate interaction: favorable cases are the sequence of H-bonds for the hydroxyl groups resulting from the water dissociation and the mode of adsorption for the ammonium ions. Lateral interactions also force the adsorbed CO₂ molecules to bend over the surface, so that their mutual orientation resembles the geometry of the CO₂ dimer.     

预硫化加氢催化剂液体钝化工艺研究

采用液态含氧烃对预硫化加氢催化剂进行钝化处理,考察了含氧烃的用量、钝化温度、钝化时间以及不饱和烃的含量对加氢催化剂钝化效果的影响;以催化柴油为原料,采用固定床连续微反装置对钝化前后的催化剂进行活性评价,同时以ONU自热测试装置对钝化的催化剂自热最高温度进行评价,确定最佳钝化工艺条件.实验结果表明,采用含氧烃对预硫化加氢催化剂进行钝化处理是可行的,最佳的钝化工艺条件为:含氧烃用量占催化剂孔体积的40%;钝化时间为10 min;钝化温度为40℃;不饱和烃含量为100%.该工艺操作简单,可有效抑制催化剂硫的脱离和自热反应,并能保持催化剂的活性,易于活化.     

SiO_2对低温液相法制备锐钛型TiO_2/SiO_2纳米复合膜性能的影响

采用浸渍提拉法在玻璃表面制得SiO2/TiO2纳米复合膜,筛选出SiO2∶TiO2优化摩尔比为0.1∶1。结果表明,加入SiO2可有效提高TiO2膜层均匀性,降低晶粒直径,纳米复合膜对甲基橙溶液光催化降解率为38.58%,光照30min后膜接触角为5(°),纳米膜与玻璃之间附着力达到1级,且对各类介质均具有良好的耐蚀性。     

Effects of boron in Co---Mo/B---Al2O3 hydrotreatment catalysts

Several mild hydrocracking 3 wt.-% Co-10 wt.-% Mo/B---Al₂O₃ catalysts have been prepared by adding H₃BO₃ into a boehmite dough during kneading + extrusion, drying and calcination prior to impregnation. HDS, HDN and cracking were monitored in the hydrotreatment of a VGO feedstock and the optimum B content was estimated around 3 wt.-%. The effects of boron on these catalysts will be discussed here with a particular focus on the effect of boron during impregnation. Using a simple hydrothermal treatment method by soxhlet, B can be extracted, with hot water, from catalysts and from supports. Simultaneously, on supports calcined at 600°C, the formation of a boehmite phase was detected after extraction.     

Organic nitrogen compounds in gas oil blends, their hydrotreated products and the importance to hydrotreatment

In the pretreatment of feeds for catalytic cracking and for HDA, the primary objective is to reduce the amount of organic sulfur and nitrogen compounds in the feedstock [Catal. Rev.-Sci. Eng. 36 (1994) 75] [1]. Organic nitrogen compounds have a significantly negative kinetic effect on hydrotreating reactions. The distribution of the organic nitrogen compounds in feed and hydrotreated products is discussed. Alkyl-substituted carbazoles are found to be the dominant and most refractive organic nitrogen compound in the feed. Our results show that indoles and quinolines are very reactive as compared with carbazoles. From the characterization of the pyrrole benzologues, it is concluded that the more the substituents, the lesser the reactivity. It is well known that conversion of organic sulfur occurs via two different mechanistic routes: the direct and the hydrogenation route [J. Catal. 61 (1981) 523; AIChE J. 27 (1981) 663; J. Catal. 97 (1986) 52; Catal. Today, in press; Polyhedron 16 (1997) 3213] [2, 3, 4, 5 and 6]. The hydrogenation route converts the most refractive S-molecules and plays a very important role in the conversion of N-compounds. N-containing molecules often show a very low reactivity as compared with the analogous sulfur compounds. Several studies using model feedstocks show that nitrogen-containing molecules, and in particular, basic organic nitrogen compounds inhibit the HDS reaction [Appl. Catal. A 170 (1998) 1] [7]. In this study, real feed experiments have demonstrated that even though carbazoles are slow to react and are among the predominant N-compounds, it is the basic N-compounds that are the major inhibiting species in diesel fuels.     

Support effects on structure and activity of molybdenum oxide catalysts for the oxidative dehydrogenation of ethane

The structural and catalytic properties of MoO₃ catalysts supported on ZrO₂, Al₂O₃, TiO₂ and SiO₂ with Mo surface densities, n_s, in the range of 0.5–18.5 Mo/nm² were studied for the oxidative dehydrogenation (ODH) of ethane by in situ Raman spectroscopy and catalytic activity measurements at temperatures of 400–540 °C. The molecular structure of the dispersed surface species evolves from isolated monomolybdates (MoO₄ and MoO₅, depending on the support) at low loadings to associated MoO_x units in polymolybdate chains at high loadings and ultimately to bulk crystalline phases for loadings exceeding the monolayer coverage of the supports used. The nature of the oxide support material and of the Mo–O–support bond has a significant influence on the catalytic behaviour of the molybdena catalysts with monolayer coverage. The dependence of reactivity on the support follows the order ZrO₂ > Al₂O₃ > TiO₂ > SiO₂. The oxygen site involved in the anchoring Mo–O–support is of relevance for the catalytic activity.     

Analysis of the hydrotreatment of Maya heavy crude with NiMo catalysts supported on TiO2-Al2O3 binary oxides: Effect of the incorporation method of Ti

Heavy Maya crude has been hydrotreated with NiMo/alumina-titania catalysts in which titania was incorporated by two different methods. Titania added to boehmite followed by calcination in order to promote formation of Ti–O–Al bonds, and Ti added to alumina in order to promote the formation of TiO₂ structures on the surface. The reaction results indicate that hydrodesulfurization (HDS), hydrodemetallization (HDM) and hydrodenitrogenation (HDN) activities are improved by the incorporation of Ti to the catalyst. In all cases, catalysts prepared by the method leading to the formation of surface TiO₂ structures show superior performance in the three functionalities (HDS, HDM and HDN). Raman analysis of the supports gives clear evidence of the differences in Ti oxide structures on the surface. The characterization of the catalysts indicates that Ti-modified catalysts have increased surface acidity (evaluated by pyridine adsorption) and greater number of coordinatively unsaturated sites (titrated by NO adsorption). Ti-containing catalysts seem to be also more stable with time-on-stream.     

固体颗粒增强化学镀铜基复合材料及其磨损研究

在铜表面上用化学镀法制备了TiO2、S iO2颗粒增强的铜基复合材料,考查了颗粒加入量和种类对复合材料耐磨性的影响。结果表明,随着镀液中颗粒含量增加,复合材料的磨损明显降低,而摩擦系数略有增加;而含S iO2复合材料磨损低于含TiO2复合材料,摩擦力高于含TiO2复合材料。     

溶胶浓度对TiO2－SiO2纳米薄膜性能的影响

采用溶胶-凝胶（Sol-Gel）法,以正硅酸乙酯（TEOS）和甲基三乙氧基硅烷（MTES）为前驱体,制备出含纳米TiO2的复合薄膜,并研究了溶胶浓度对薄膜色度、光泽、憎水、耐酸碱等性能的影响。对实验结果进行正交评价,甄选出溶胶豹最佳浓度。结论：对于注重图案和光泽保护的器物,建议溶胶浓度选取30％左右：对于注重防水防潮保护的器物,建议浓度在50％～70％区间进行选择：当溶胶浓度选取50％以上时,材料耐酸碱性能优越：综上,当杂化材料浓度为50％时,综合性能最佳。     

钛硅体系的制备与特性

采用水解法制备二氧化硅掺杂的二氧化钛体系；用X射线衍射、激光粒度仪、IR对其进行表征；观察其对甲基橙的光催化性能，并与纯二氧化钛体系性能对此；结果表明掺杂改变了钛硅结合，最小粒度有最好催化性能。     

层间组装SiO2-TiO2粘土材料的制备与表征

以(C2H5O)4Si和Ti(OC4H9)4为硅源和钛源,采用溶胶-凝胶法制备SiO2-TiO2柱化剂,将原土直接加入柱化剂进行柱化反应得到SiO2-TiO2柱撑蒙脱土,对其进行结构和性能表征,考察了柱化剂中Si/Ti比、柱化剂/原土比、柱化反应条件(反应温度和超声处理)及热处理温度对其结构和性能的影响. 结果表明,SiO2-TiO2柱体成功进入蒙脱土层间,在除去未参与柱化反应的柱化剂的条件下,比表面积可达127.2 m2/g,热稳定性提高了70℃,柱化剂中Si含量增加有利于热稳定性的提高,500℃以下焙烧的SiO2-TiO2柱体中Ti以钛氧四面体和八面体形式存在,600℃焙烧可形成锐钛矿晶型.     

In situ XAFS analysis of Pd–Pt catalysts during hydrotreatment of model oil

Supported Pd–Pt catalysts are efficient for hydrodesulfurization (HDS) and hydrodearomatization (HDA) reactions of diesel fuel and their activity varied with the kinds of supports. Concerning HDA, alumina supported catalysts showed four times higher TOF (turn over frequency) than silica supported one. In order to elucidate the difference in activity, the structural analysis of the active phase was performed. After reduction pretreatment, relatively uniform and large metallic alloy Pd–Pt particles were formed on SiO₂, whereas, Pd and Pt atoms formed rather segregated particles on Al₂O₃. Subsequent X-ray absorption of fine structure (XAFS) analysis under HDS conditions showed no contribution of sulfur for SiO₂ supported catalyst, whereas, formation of sulfided metal species was observed in XAFS spectra for the Al₂O₃ supported catalyst. It is suggested that on Pd–Pt/SiO₂, thin sulfide layer on the metal cluster surface blocked the active sites and lowered the HDA activity. Presence of partially sulfided phase originated from rather segregated structure like Pd–Pt/Al₂O₃ is thought to be requisite for high HDA activity.     

Effects of carbon on the sulfidation and hydrodesulfurization of CoMo hydrating catalysts

The effects of carbon addition on CoMo catalyst performance for sulfidation and hydrodesulfurization (HDS) were investigated. The carbon-containing catalyst was prepared by impregnation of γ-Al₂O₃ support with NH₃ aqueous solution containing Co(NO₃)₂·6H₂O, (NH₄)₆Mo₇O₂₄·4H₂O and ethylenediamine. The results indicated that the incorporation of proper carbon on CoMo catalyst can improve its HDS performance. The carbon species on the catalyst were characterized by temperature-programmed oxidation and reduction, temperature-programmed desorption of ammonia and ultraviolet-visible diffuse reflectance spectra. Two forms of carbon species were differentiated: one is spread over the catalyst surface, similar to coke formed from reaction; the other interacts with active phase as an intermediate support. The carbon species acting as intermediate support may decrease the interaction of active metals with support, which enhances the sulfidation and HDS activities of CoMo catalyst. This work was presented at the 7th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

硅微粉对MgO-SiO2-H2O系统中水合物形成的影响

采用差热和热重分析,X射线衍射分析,X射线光电子能谱分析技术,对MgO-SiO2-H2O系统中经110℃,24 h热处理后的试样进行了研究.结果表明由于微米SiO2的高活性,可能有某种MgO-SiO2-H2O系水合物存在.     

Inhibition of CoMo/HMS catalyst deactivation in the HDS of 4,6-DMDBT by support modification with phosphate

A series of CoMoS catalysts supported on hexagonal mesoporous silica (HMS) modified with different amounts of phosphate (0.5, 1.0, 1.5 and 2.0 wt.%) were prepared in order to study the influence of phosphate on catalyst deactivation. The catalysts were characterized by a variety of techniques (X-ray fluorescence, N₂ adsorption-desorption at 77 K, FT-IR study of the framework vibration and NO adsorption, NH₃-TPD, H₂-TPR, XPS, ³¹P NMR and TPO/TGA). The sulfided catalysts were tested in the deep hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene (4,6-DMDBT) performed in a fixed-bed flow reactor at 598 K, P = 5.0 MPa and WHSV = 46.4 h⁻¹. The catalyst with the largest phosphate content (2.0 wt.%) showed the best catalytic response linked with its low deactivation during on-stream reaction and a larger sulfidation degree of Co species. It was found that coking behavior is closely related with the location of the active sites in the support structure being a lower coke formation on the catalysts having active phases located within support structure. The catalysts modified with a large amount of phosphorous (1.5 and 2.0 wt.% of P₂O₅) were more susceptible to coking and produced a more polymerized coke than P-free sample, as confirmed by TPO/TGA experiments. The presence of P₂O₅ favours the sulfidation degree of Co species and the creation of medium strength acid sites leading to the enhancement of the 4,6-DMDBT HDS reaction toward the isomerization route.     

Ti-modified alumina supports prepared by sol–gel method used for deep HDS catalysts

The typical physico-chemical properties and their hydrodesulfurization activities of NiMo/TiO₂-Al₂O₃ series catalysts with different TiO₂ loadings were studied. The catalysts were evaluated with a blend of two kinds of commercially available diesels in a micro-reactor unit. Many techniques including N₂-adsorption, UV–vis DRS, XRD, FT-Raman, TPR, pyridine FT-IR and DRIFT were used to characterize the surface and structural properties of TiO₂-Al₂O₃ binary oxide supports and the NiMo/TiO₂-Al₂O₃ catalysts. The samples prepared by sol–gel method possessed large specific surface areas, pore volumes and large average pore sizes that were suitable for the high dispersion of nickel and molybdenum active components. UV–vis DRS, XRD and FT-Raman results indicated that the presence of anatase TiO₂ species facilitated the formation of coordinatively unsaturated sites (CUS) or sulfur vacancies, and also promoted high dispersion of Mo active phase on the catalyst surfaces. DRIFT spectra of NO adsorbed on the pure MoS₂ and the catalysts with TiO₂ loadings of 15 and 30% showed that NiMo/TiO₂-Al₂O₃ catalysts possessed more CUS than that of pure MoS₂. HDS efficiencies and the above characterization results confirmed that the incorporation of TiO₂ into Al₂O₃ could adjust the interaction between support and active metals, enhanced the reducibility of molybdenum and thus resulted in the high activity of HDS reaction.