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1.
The effect of the TiO 2–Al 2O 3 mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous HDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO 2 into the support, and particularly over rich- and pure-TiO 2-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO 2. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil HDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO 2 content and large differences are observed between the catalysts supported on pure Al 2O 3 and pure TiO 2. In contrast, in the case of the thiophene test, the pure Al 2O 3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al 2O 3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al 2O 3- and pure TiO 2-based catalysts is relatively small and dependent on the H 2 pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H 2 partial pressure on the thiophene HDS, and on the effect of H 2S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking. 相似文献
2.
Catalytic activities of Al 2O 3–TiO 2 supporting CoMo and NiMo sulfides (CoMoS and NiMoS) catalysts were examined in the transalkylation of isopropylbenzene and hydrogenation of naphthalene as well as the hydrodesulfurization (HDS) of model sulfur compounds, conventional gas oil (GO), and light cycle oil (LCO). Al 2O 3–TiO 2 supporting catalysts exhibited higher activities for these reactions except for the HDS of the gas oil than a reference Al 2O 3 supporting catalyst, indicating the correlation of these activities. Generally, more content of TiO 2 promoted the activities. Inferior activity of the catalyst for HDS of the gas oil is ascribed to its inferior activity for HDS of dibenzothiophene (DBT) in gas oil as well as in model solvent decane, while the refractory 4,6-dimethyldibenzothiophene (4,6-DMDBT) in gas oil as well as in decane was more desulfurized on the catalyst. Characteristic features of Al 2O 3–TiO 2 catalyst are discussed based on the paper results. 相似文献
3.
Sulfidation of trimetallic CoNiMo/Al 2O 3 catalysts was studied by thermogravimetry at 400 °C under flow and pressure conditions. Results were compared with those obtained on prepared and industrial CoMo/Al 2O 3 and NiMo/Al 2O 3 catalysts. The amount of sorbed H 2S on the sulfided solids was measured at 300 °C in the H 2S pressure range 0–3.5 MPa at constant H 2 pressure (3.8 MPa). The adsorption isotherms were simulated using a model featuring dissociated adsorption of H 2S on supported metal sulfides and bare alumina. The amount of sulfur-vacancy sites could thus be determined under conditions close to industrial practice. A relationship with activity results for thiophene HDS and benzene hydrogenation was sought for. 相似文献
4.
The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al 2O 3) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir–Hinshelwood (L–H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al 2O 3 catalysts) on the initial reaction rate. The L–H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al 2O 3 catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al 2O 3 or the presulphided NiMo/Al 2O 3 catalyst. 相似文献
5.
CoMo on Al 2O 3 catalyst prepared by spray pyrolysis method was found in the form of spheres of 0.5–1.2 μm, which consisted of tiny primary particles of ca. 10–20 nm diameter. The materials shows comparable activity to those of commercial catalysts in HDS of straight run gas oil, in particular, refractory 4,6-dimethyldibenzothiophene (4,6-DMDBT). Weaker interactions between CoMo and Al 2O 3 are suggested by temperature-programmed reduction (TPR), Raman spectroscopy, to give more active species than those over the impregnated catalysts. This accounts for its comparable activity in spite of its smaller surface area. 相似文献
6.
The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activity of a series of NiMo/Al 2O 3 catalyst containing boron (B) and phosphorus (P) were tested in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen. Detailed characterization of these catalysts is given in Part I of this paper. Addition of B and P caused the formation of extremely strong acid sites on the catalyst and enhanced its HDN activity. The total (TN), basic (BN) and non-basic nitrogen (NBN) conversions increased from 61.9 to 78.0 wt.%, from 78.9 to 93.0 wt.% and from 52.8 to 70.0 wt.%, respectively, with the increase in B concentration from 0 to 1.7 wt.% to NiMo/Al 2O 3 catalyst. Similarly, TN, BN and NBN conversions increased from 61.9 to 78.4 wt.%, from 78.9 to 91.0 wt.%, and from 52.8 to 71.6 wt.% with the addition of 2.7 wt.% P. Though the addition of B and P to NiMo/Al 2O 3 catalyst did not show any significant effect on S conversion, the HDN and HDS activities of the catalyst containing 1.7 wt.% B and the one containing 2.7 wt.% P are comparable to those of a commercial catalyst. The activity over extended period indicated that catalysts L and K were more stable (lower deactivation rate) in terms of nitrogen removal activity than catalyst B (reference catalyst). On the other hand, the stability for sulfur removal was comparable with catalyst B. Selected catalysts after use were characterized using BET surface area, TPR, TPD and SEM techniques which were correlated further with their activities. 相似文献
7.
以中和法合成的不同SiO 2含量的改性氧化铝为载体,本文制备系列Si改性的NiMo/Al 2O 3催化剂,采用X射线衍射(XRD)、N 2物理吸附(BET)、程序升温脱附(NH 3-TPD)、吡啶吸附红外光谱(Py-IR)、程序升温还原(H 2-TPR)、高分辨透射电镜(HRTEM)和X射线光电子能谱(XPS)等分析手段进行详细表征。表征结果显示,引入Si减弱了活性金属与载体之间的相互作用,改善了催化剂的孔结构与表面酸性分布,提高了活性相分散度和金属硫化度,促使形成更多的II类NiMoS活性相。以二苯并噻吩(DBT)为模型化合物,在固定床加氢装置上考察了系列催化剂的加氢脱硫(HDS)性能,结果表明,引入Si可降低DBT的加氢反应活化能,提高反应速率常数,进而提高催化剂的加氢脱硫活性。对比DBT转化率在50%时的脱硫产物分布表明引入Si可影响催化剂的反应路径选择性,直接脱硫路径(DDS)选择性从83.69%增加至92.89%,证实了催化剂的表征规律。 相似文献
8.
Alumina–titania supports containing 5–50 wt.% of TiO 2 were prepared by coprecipitation method using inorganic precursors (sodium aluminate and titanium chloride). DTA-TGA, XRD, SEM, TPD NH3, and IR spectroscopy were used to characterise these materials. The study shows that the promoting effect of nickel on the HDS activity of molybdenum catalysts supported on Al 2O 3TiO 2 is significantly lower than that for molybdenum catalyst supported on Al 2O 3, and depends on the TiO 2 content. The SEM results show that in the case of rich Al support (20 wt.% of TiO 2) molybdenum was aggregated on the external surface of the catalyst, whereas it was uniformly dispersed on the external surface of alumina. Results also show that molybdenum is preferably supported on aluminum oxide. Application of Al 2O 3TiO 2 oxides enhances the HDN activity of nickel–molybdenum catalysts. The highest HDN efficiency was obtained for the NiMo/Al 2O 3TiO 2 catalyst containing 50 wt.% of TiO 2. HDN activity was found to depend on protonic acidity and anatase content. 相似文献
9.
采用分步浸渍法制备了不同磷添加方式改性的NiMo/Al 2O 3催化剂,在固定床微反装置上考察了该系列催化剂对焦炉煤气中噻吩加氢脱硫(HDS)性能的影响,采用BET、X射线衍射(XRD)、H 2程序升温还原(H 2-TPR)、NH 3程序升温脱附(NH 3-TPD)、C 4H 4S(H 2)程序升温脱附[C 4H 4S(H 2)-TPD]、X射线光电子能谱(XPS)、高清透射电镜(HRTEM)和拉曼(Raman)等分析手段对催化剂进行表征。结果表明,不同磷添加方式制备NiMo/Al 2O 3催化剂的HDS性能存在较大差异。其中,催化剂PNi-Mo/Al和PMo-Ni/Al表面弱吸附解离活性位增强,对焦炉煤气中噻吩有较好的低温加氢脱硫活性,以含292.5mg/m 3噻吩的模拟焦炉煤气为原料时,PNi-Mo/Al在250℃下对噻吩的脱硫率达61%。对于PNi-Mo/Al和PMo-Ni/Al催化剂,先浸渍P、Ni或者P、Mo时,P优先和载体Al 2O 3作用,减弱了活性金属组分Ni、Mo与载体间的相互作用,而又防止Ni或者Mo与载体间相互作用过低而聚集,提高了Ni、Mo在载体表面的均匀分散,生成能够促进硫化形成Ⅱ型活性相Ni-Mo-S的NiMoO 4物种。NiMoO 4和MoO 3之间的协同作用提高了催化剂的硫化度,使HDS活性得以提高。 相似文献
10.
A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions:200 °C, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst (SC) had aromatic structure, composed of carbon enriched inner core, and oxygen-containing (SO3H, COOH, OH) groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts (strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five (HZSM-5), sulfated zir-conia) in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively. 相似文献
11.
CoMo and NiMo catalysts were prepared and the catalytic activities were evaluated in fixed bed micro-flow and bench-scale reactors with different feed composition. Experiments were conducted at conditions close to those that exist in the industrial practice. Due to the different nature of the feeds, the conditions were varied with respect to both evaluation scales. The fresh and spent catalysts were characterized. Spent catalyst textural properties indicated that catalysts were deactivated and the surface area and pore volume dropped by 20–60%. The adsorption–desorption hysteresis of spent catalysts indicated that cylindrical pores are deactivated at the pore mouth and played an important role in modification by either closing one end of the pore or forming a narrow neck pore, which is indicative of the formation of “ ink-bottle” type pores. Thus, the deposition of metal and carbon takes place preferentially at the pore entrance, which causes pore mouth plugging. These results are also supported by the SEM–EDAX analysis, where metal and carbon depositions are evident and taking place at the superficial region of a catalyst particle. The increase in absolute area of hysteresis is based on the catalyst's average pore diameter: the higher the average pore diameter, the lower the area of the spent catalyst. The activity and deactivation of the catalyst are discussed on the basis of catalyst porosity and deposited metal characterization. The composition of catalysts varies, considering two applications in a multi-reactor system: a CoMo catalyst for the first reactor, and a NiMo in the second reactor; the former is supported on γ-Al 2O 3 and the latter on TiO 2/Al 2O 3. As a comparison, the CoMo catalyst exhibited better hydrogenolysis while the NiMo catalyst showed better hydrogenation activity in both micro-flow and bench-scale reactors. It appears that there is a moderate effect of TiO 2 content in support on Ni and V hydrodemetallization (HDM) while hydrodeasphaltenization (HDAs) and hydrodesulfurization (HDS) activities were slightly improved when a partially hydrotreated feed, which contains more refractory compounds than virgin feedstock, was employed. 相似文献
12.
Hydrotreating of Maya heavy crude oil over high specific surface area CoMo/TiO 2–Al 2O 3 oxide supported catalysts was studied in an integral reactor close to industrial practice. Activity studies were carried out with Maya crude hydrodesulfurization (HDS), hydrodemetallization (HDM), hydrodenitrogenation (HDN), and hydrodeasphaltenization (HDAs) reactions. The effect of support composition, the method of TiO 2 incorporation, and the catalyst deactivation are examined. Supported catalysts are characterized by BET specific surface area (SSA), pore volume (PV), pore size distribution (PSD), and atomic absorption. It has been found that sulfided catalysts showed a wide range of activity variation with TiO 2 incorporation into the alumina, which confirmed that molybdenum sulfided active phases strongly depend on the nature of support. The pore diameter and nature of the active site for HDS, HDM, HDN, and HDAs account for the influence of the large reactant molecules restricted diffusion into the pore, and/or the decrease in the number of active sites due to the MoS 2 phases buried with time-on-stream. The textural properties and hysteresis loop area of supported and spent catalysts indicated that catalysts were deactivated at the pore mouth due to the metal and carbon depositions. The atomic absorption results agreed well regarding the textural properties of spent catalysts. Thus, incorporation of TiO 2 with γ-Al 2O 3 alters the nature of active metal interaction with support, which may facilitate the dispersion of active phases on the support surface. Therefore, the TiO 2 counterpart plays a promoting role to HDS activity due to the favorable morphology of MoS 2 phases and metal support interaction. 相似文献
13.
Water formed during hydrotreating of oxygen-containing feeds has been found to affect the performance of sulphided catalysts in different ways. The effect of water on the activity of sulphided NiMo/γ-Al 2O 3 and CoMo/γ-Al 2O 3 catalysts in hydrodeoxygenation (HDO) of aliphatic esters was investigated in a tubular reactor by varying the amount of water in the feed. In additional experiments, H 2S was added to the feed, alone and simultaneously with water. Under the same conditions, the NiMo catalyst exhibited a higher activity than the CoMo catalyst. The ester conversions decreased with increase in the amount of added water. When H2S and water were added simultaneously, the conversion increased to the same level as without water addition on the NiMo catalyst and reached a higher value on the CoMo catalyst. The conversions were highest, however, when only H2S was added. Unfortunately, the conversions decreased with time under all conditions. On both catalysts, the total yield of the C7 and C6 hydrocarbons decreased with the amount of added water, while the concentrations of the oxygen-containing intermediates increased. The presence of H2S improved the total hydrocarbon yield and shifted the main products towards the C6 hydrocarbons. Thus, the addition of H2S effectively compensated the inhibition by water. 相似文献
14.
High surface area (>300 m 2 g −1) nano-structured TiO 2 oxides (ns-T) were used as CoMo hydrodesulfurization catalyst support. Cylindrical extrudates were impregnated by incipient wetness with Mo (2.8 Mo at. nm −2) and Co (atomic ratio Co/(Co + Mo) = 0.3). Characterization of impregnated precursors was carried out by N 2 physisorption, XRD and atomic absorption and laser-Raman spectroscopies. Sulfided catalysts (400 °C, H 2S/H 2) were studied by X-ray photoelectronic spectroscopy. As indicated by XRD and after various preparation steps (extrusion, Mo and Co impregnation and sulfiding) the nano-structured material was well preserved. XPS analyses showed that Co and Mo dispersion over the ns-T support was much higher than that on alumina. Very high surface S concentration suggested that even ns-T was partially sulfided during catalyst activation. Dibenzothiophene hydrodesulfurization activity (5.73 MPa, 320 °C, n-hexadecane as solvent) of CoMo/ns-T was two-fold to that of an alumina-supported commercial CoMo catalyst. The improvement was even more remarkable in intrinsic pseudo kinetic constant basis. No important differences in selectivity over the catalysts supported on either Al 2O 3 or ns-T were observed, where direct desulfurization to biphenyl was favored. Both Mo dispersion and sulfidability were enhanced on the ns-T support where Mo 4+ fraction was notably increased (100%) as to that found on CoMo/Al 2O 3. 相似文献
15.
The present paper gives a detailed review of the different studies under investigation in our laboratory concerning the use of TiO 2 and TiO 2–Al 2O 3 composites prepared by chemical vapor deposition (CVD) as support for sulfide catalysts in the HDS of dibenzothiophene (DBT) derivatives. The supports investigated here are: TiO 2 (from Degussa, 50 m 2/g), Al 2O 3 (Nikki, 186 m 2/g) and TiO 2–Al 2O 3 supports prepared by CVD of TiCl 4 on alumina. Using several characterization techniques, we have demonstrated that the support composite presents a high dispersion of TiO 2 over γ-Al 2O 3 without forming precipitates up to ca. 11 wt.% loading. Moreover, the textural properties of the support composite are comparable to those of alumina. XPS investigations of Mo and NiMo catalysts supported on the different carriers show that Mo-oxide species exhibit a higher degree of sulfidation on the surface of TiO 2 and TiO 2–Al 2O 3 than on alumina. The HDS tests of 4,6-DMDBT under mild operating conditions (573 K, 3 MPa) show that sulfide catalysts supported on the composite support (ca. 11 wt.%) are more active than those supported on to TiO 2 or Al 2O 3. This higher HDS catalytic activity is attributed to the promotion of the hydrodesulfurization pathway, whereby the pre-hydrogenation of one of the aromatic rings adjacent to the thiophenic one may reduce the steric hindrance caused by the two methyl groups adjacent to the sulfur atom during the C–S bond cleavage. 相似文献
16.
The effect of the kind of ruthenium precursor {Ru 3(CO) 12 or RuCl 3· nH 2O} and the activation conditions on the performance of Ru/MgF 2 preparations in thiophene hydrodesulfurization has been studied. The highest activity, higher than that of the commercially available system CoMo/Al 2O 3, was revealed by the Ru/MgF 2 catalyst sulfided in the 50% H 2S/He atmosphere. According to the results of TPR study, this preparation was characterized by exceptionally high content of RuS 2, which seems to be responsible for its high activity. As follows from the product distribution of thiophene HDS, the activation in the H 2S/He atmosphere mainly leads to the formation of saturated products (butane), while the activation in the atmosphere of H 2S/H 2, to the formation of unsaturated products (butene-1, cis- and trans-butene-2). 相似文献
17.
A series of phosphorus promoted γ-Al 2O 3 supported NiMo carbide catalysts with 0–4.5 wt.% P, 13 wt.% Mo and 2.5 wt.% Ni were synthesized and characterized by elemental analysis, pulsed CO chemisorption, BET surface area measurement, X-ray diffraction, near-edge X-ray absorption fine structure, DRIFT spectroscopy of CO adsorption and H 2 temperature programmed reduction. X-ray diffraction patterns and CO uptake showed the P addition to NiMo/γ-Al 2O 3 carbide, increased the dispersion of β-Mo 2C particles. DRIFT spectra of adsorbed CO revealed that P addition to NiMo/γ-Al 2O 3 carbide catalyst not only increases the dispersion of Ni-Mo carbide phase, but also changes the nature of surface active sites. The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities of these P promoted NiMo/γ-Al 2O 3 carbide catalysts were performed in trickle bed reactor using light gas oil (LGO) derived from Athabasca bitumen and model feed containing quinoline and dibenzothiophene at industrial conditions. The P added NiMo/γ-Al 2O 3 carbide catalysts showed enhanced HDN activity compared to the NiMo/γ-Al 2O 3 catalysts with both the feed stocks. The P had almost no influence on the HDS activity of NiMo/γ-Al 2O 3 carbide with LGO and dibenzothiophene. P addition to NiMo/γ-Al 2O 3 carbide accelerated CN bond breaking and thus increased the HDN activity. 相似文献
18.
Al 2O 3–SiO 2 mixed oxide has been investigated as a support for hydrotreating catalyst with variation of its composition [Si/(Si + Al) = 0.06, 0.12, 0.31, 0.56, 0.78] and its interaction with the surface active metals (NiMo). The composition of support and surface species (NiMo) of catalysts were characterized by specific surface area, atomic absorption, SEM-EDX, XRD, temperature programmed reduction (TPR), Raman analysis, scanning electron microscopy (STEM) and transmission electron microscopy (TEM). Incorporation of SiO 2 in Al 2O 3 promotes a weak interaction between the active phases and particularly catalyst that predominated with SiO 2 content. The oxide and sulfided catalysts characterization indicated that the effect of support is responsible to form different catalytic sites. Crystallization of MoO 3 phases and a relatively longer crystal of MoS 2 in the sulfided catalyst were attributed to an increasing SiO 2 content in the support. The catalytic behavior of the NiMo supported catalysts is explained in terms of structural changes on the surface due to the support and active metal interactions. The activity of the different catalysts evaluated in the thiophene hydrodesulfurization reaction was higher for the catalyst having lower SiO 2 content in the support. 相似文献
19.
Accelerated deactivation tests of a laboratory prepared Co–Mo/Al 2O 3 catalyst were performed using three kinds of petroleum feedstocks. A high reaction temperature employed in the accelerated aging resulted in large amounts of carbonaceous deposition with high aromaticity, which were found to be the major deactivation cause. However, the effect of carbonaceous deposition during accelerated deactivation tests might have been overestimated compared with that during practical hydrotreating. When the catalysts were aged in a H 2S/H 2 stream without petroleum under the same reaction conditions, the crystal growth of MoS 2 layered structures was significant, but this rather resulted in an increase of both k (HDS) and k (HY). It was also suggested that the crystal growth during a commercial hydrotreating run was unlikely to be the major cause of catalyst deactivation. 相似文献
20.
The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH 4 traces under lean-burn conditions was studied in the presence or the absence of water or H 2S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H 2S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H 2S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H 2S-poisoned Pd/Al 2O 3 catalyst was studied by TPD in O 2/He. Poisoning species decompose above 873 K as SO 2 and O 2 in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O 2/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H 2S-poisoned Pd/Al 2O 3. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested. 相似文献
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