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1.
A series of phosphorus promoted γ-Al2O3 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 H2 temperature programmed reduction. X-ray diffraction patterns and CO uptake showed the P addition to NiMo/γ-Al2O3 carbide, increased the dispersion of β-Mo2C particles. DRIFT spectra of adsorbed CO revealed that P addition to NiMo/γ-Al2O3 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-Al2O3 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-Al2O3 carbide catalysts showed enhanced HDN activity compared to the NiMo/γ-Al2O3 catalysts with both the feed stocks. The P had almost no influence on the HDS activity of NiMo/γ-Al2O3 carbide with LGO and dibenzothiophene. P addition to NiMo/γ-Al2O3 carbide accelerated CN bond breaking and thus increased the HDN activity.  相似文献   

2.
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.  相似文献   

3.
采用共浸渍和氢气程序升温还原法, 以γ-Al2O3为载体,制备负载W质量分数30%(以WO3计)的磷化钨催化剂,对催化剂进行XRD、BET、SEM和TG/DTA表征,考察催化剂的C5石油树脂加氢反应性能,并研究助剂Ni和Co对催化剂结构和加氢反应活性的影响。结果表明,助剂的加入能改善催化剂表面活性组分的分散性和增加WP/γ-Al2O3催化剂的比表面积,对WP/γ-Al2O3催化剂活性组分与载体之间的相互作用也可能存在影响,Co或Ni对磷化钨催化剂C5石油树脂加氢反应均有不同程度的改善作用。  相似文献   

4.
Development of new catalysts for deep hydrodesulfurization of gas oil   总被引:3,自引:0,他引:3  
TiO2–Al2O3 composite supports have been prepared by chemical vapor deposition (CVD) over γ-Al2O3 substrate, using TiCl4 as the precursor. High dispersion of TiO2 overlayer on the surface of Al2O3 has been obtained, and no cluster formation has been detected. The catalytic behavior of Mo supported on Al2O3, TiO2 and TiO2–Al2O3 composite has been investigated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the Mo catalysts supported on TiO2–Al2O3 composite, in particular for the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) is much higher than that of conversion obtained over Mo catalyst supported on Al2O3. The ratio of the corresponding cyclohexylbenzenes/biphenyls is increased over Mo catalyst supported on TiO2–Al2O3 composite support. This means that the reaction rate of prehydrogenation of an aromatic ring rather than the rate of hydrogenolysis of C–S bond cleavage is accelerated for the HDS of DBT derivatives. The Mo/TiO2–Al2O3 catalyst leads to higher catalytic performance for deep HDS of gas oil.  相似文献   

5.
Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H2 and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH3-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO2, γ-Al2O3 supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al2O3 catalyst. The WP/γ-Al2O3 catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO2 catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al2O3 catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al2O3 catalyst. In general, a support or promoter in the WP/γ-Al2O3 catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.  相似文献   

6.
Mo---Co or Mo---Ni catalysts supported on alumina (Al2O3) have been widely used for hydrodesulfurization (HDS) of heavy petroleum fractions. In order to enhance the catalytic activities for HDS, a composite type support (TiO2-Al2O3) prepared by the chemical vapor deposition (CVD) method has been studied. We found that Mo catalyst supported on TiO2-Al2O3 showed much higher catalytic activity for HDS of dibenzothiophene derivatives than the catalysts supported on Al2O3.  相似文献   

7.
The effect of the TiO2–Al2O3 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 TiO2 into the support, and particularly over rich- and pure-TiO2-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO2. 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 TiO2 content and large differences are observed between the catalysts supported on pure Al2O3 and pure TiO2. In contrast, in the case of the thiophene test, the pure Al2O3-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 Al2O3-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 Al2O3- and pure TiO2-based catalysts is relatively small and dependent on the H2 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 H2 partial pressure on the thiophene HDS, and on the effect of H2S 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   

8.
MgO-supported Mo, CoMo and NiMo sulfide hydrotreating catalysts   总被引:2,自引:0,他引:2  
The most common preparation of high surface area MgO (100–500 m2 g−1) is calcination of Mg(OH)2 obtained either by precipitation or MgO hydration or sol–gel method. Preparation of MoO3/MgO catalyst is complicated by the high reactivity of MgO to H2O and MoO3. During conventional aqueous impregnation, MgO is transformed to Mg(OH)2, and well soluble MgMoO4 is easily formed. Alternative methods, that do not impair the starting MgO so strongly, are non-aqueous slurry impregnation and thermal spreading of MoO3. Mo species of MoO3/MgO catalyst are dissolved as MgMoO4 during deposition of Co(Ni) by conventional aqueous impregnation. This can be avoided by using non-aqueous impregnation. Co(Ni)Mo/MgO catalysts must be calcined only at low temperature because Co(Ni)O and MgO easily form a solid solution. Literature data on hydrodesulfurization (HDS) activity of MgO-supported catalysts are often contradictory and do not reproduced well. However, some results suggest that very highly active HDS sites can be obtained using this support. Co(Ni)Mo/MgO catalysts prepared by non-aqueous impregnation and calcined at low temperature exhibited strong synergism in HDS activity. Co(Ni)Mo/MgO catalysts are much less deactivated by coking than their Al2O3-supported counterparts. Hydrodenitrogenation (HDN) activity of Mo/MgO catalyst is similar to the activity of Mo/Al2O3. However, the promotion effect of Co(Ni) in HDN on Co(Ni)Mo/MgO is lower than that on Co(Ni)Mo/Al2O3.  相似文献   

9.
Hydrotreating of Maya heavy crude oil over high specific surface area CoMo/TiO2–Al2O3 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 TiO2 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 TiO2 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 MoS2 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 TiO2 with γ-Al2O3 alters the nature of active metal interaction with support, which may facilitate the dispersion of active phases on the support surface. Therefore, the TiO2 counterpart plays a promoting role to HDS activity due to the favorable morphology of MoS2 phases and metal support interaction.  相似文献   

10.
This article describes a novel hydrothermal deposition method for preparing highly dispersed NiW/γ-Al2O3 catalysts and demonstrates its advantages over the conventional impregnation method. Via the hydrothermal precipitation reactions between sodium tungstate and hydrochloric acid and between nickel nitrate and urea, respectively, the active species W and Ni were deposited on γ-Al2O3. In the hydrothermal deposition of WO3, a surfactant hexadecyltrimethyl ammonium bromide (CTAB) was used to prevent the aggregation of WO3. The characterization results obtained by means of X-ray photoelectron spectroscopy (XPS), N2 adsorption and high-resolution transmission electron microscopy (HRTEM) measurements showed that compared with the catalyst prepared by the conventional impregnation method, the catalyst with the same metal contents prepared by the hydrothermal deposition had much higher W and Ni dispersion, higher specific surface area, larger pore volume, the significantly decreased slab length and slightly increased stacking degree of sulfided W species, leading to the significantly enhanced dibenzothiophene (DBT) hydrodesulfurization (HDS) activity. The DBT HDS assessment results also revealed that the catalyst containing 17.7 wt% WO3 and 2.4 wt% NiO prepared by the hydrothermal deposition method had the similar DBT HDS activity as a commercial NiW/γ-Al2O3 catalyst containing 23 wt% WO3 and 2.6 wt% NiO, resulting in the greatly decreased amount of active metals for achieving the same HDS activity.  相似文献   

11.
A series of Re-containing catalysts supported on activated carbon, with Re loading between 0.74 and 11.44 wt.% Re2O7, was prepared by wet impregnation and tested in the simultaneous hydrodesulphurisation (HDS) and hydrodenitrogenation (HDN) of a commercial gas oil. Textural analysis, XRD, X-ray photoelectron spectroscopy (XPS) and surface acidity techniques were used for physicochemical characterisation of the catalysts. Increase in the Re concentration resulted in a rise in the HDS and HDN activity due to the formation of a monolayer structure of Re and the higher surface acidity. At Re concentrations >2.47 wt.% Re2O7 (0.076 Re atoms nm−2) the reduction in the catalytic activity was related to the loss in specific surface area (BET) due to reduction in the microporosity of the carbon support. The magnitude of the catalytic effect was different for HDS and HDN, and depended strongly on the Re content and reaction temperature. The apparent activation energies were about 116–156 kJ mol−1 for HDS and 24–30 kJ mol−1 for HDN. This led to a marked increase in the HDN/HDS selectivity with decreasing temperature (values >3 at 325 °C), due to the large differences in the apparent activation energies of HDS and HDN found for all catalysts. A gradual increase in the HDN/HDS selectivity with increased Re loading was also found and related to the observed increase of catalyst acidity. The results are compared with those obtained for a series of Re/γ-Al2O3 catalysts.  相似文献   

12.
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   

13.
Composite types of TiO2–Al2O3 supports, which are γ-aluminas coated by titania, have been prepared by chemical vapor deposition (CVD), using TiCl4 as a precursor. Then supported molybdenum catalysts have been prepared by an impregnation method. As supports, we employed γ-alumina, anatase types of titania, and composite types of TiO2–Al2O3 with different loadings of TiO2. We studied the conversion of Mo from oxidic to sulfidic state through sulfurization by X-ray photoelectron spectroscopy (XPS). The obtained spectra unambiguously revealed the higher reducibility from oxidic to sulfidic molybdenum species on the TiO2 and TiO2–Al2O3 supports compared to that on the Al2O3 support. Higher TiO2 loadings of the TiO2–Al2O3 composite support led to higher reducibility for molybdenum species. Furthermore, the catalytic behavior of supported molybdenum catalysts has been investigated for hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the TiO2–Al2O3 supported Mo catalysts, in particular for the 4,6-dimethyl-DBT, is much higher than that obtained over Al2O3 supported Mo catalyst. The ratio of the corresponding cyclohexylbenzene (CHB)/biphenyl (BP) derivatives is increased over the Mo/TiO2–Al2O3. This indicates that the prehydrogenation of an aromatic ring plays an important role in the HDS of DBT derivatives over TiO2–Al2O3 supported catalysts.  相似文献   

14.
Catalytic activities of Al2O3–TiO2 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). Al2O3–TiO2 supporting catalysts exhibited higher activities for these reactions except for the HDS of the gas oil than a reference Al2O3 supporting catalyst, indicating the correlation of these activities. Generally, more content of TiO2 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 Al2O3–TiO2 catalyst are discussed based on the paper results.  相似文献   

15.
The siliceous and the metal substituted (B or Al)-SBA-15 molecular sieves were used as a support for NiMo hydrotreating catalysts (12 wt.% Mo and 2.4 wt.% Ni). The supports were characterized by X-ray diffraction (XRD), scanning electron microscopy and N2 adsorption–desorption isotherms. The SBA-15 supported NiMo catalysts in oxide state were characterized by BET surface area analysis and XRD. The sulfided NiMo/SBA-15 catalysts were examined by DRIFT of CO adsorption and TPD of NH3. The HDN and HDS activities with bitumen derived light gas oil at industrial conditions showed that Al substituted SBA-15 (Al-SBA-15) is the best among the supports studied for NiMo catalyst. A series of NiMo catalysts containing 7–22 wt.% Mo with Ni/Mo weight ratio of 0.2 was prepared using Al-SBA-15 support and characterized by BET surface area analysis, XRD and temperature programmed reduction and DRIFT spectroscopy of adsorbed CO. The DRIFT spectra of adsorbed CO showed the presence of both unpromoted and Ni promoted MoS2 sites in all the catalysts, and maximum “NiMoS” sites concentration with 17 wt.% of Mo loading. The HDN and HDS activities of NiMo/Al-SBA-15 catalysts were studied using light gas oil at temperature, pressure and WHSV of 370 °C, 1300 psig and 4.5 h−1, respectively. The NiMo/Al-SBA-15 catalyst with 17 wt.% Mo and 3.4 wt.% of Ni is found to be the best catalyst. The HDN and HDS activities of this catalyst are comparable with the conventional Al2O3 supported NiMo catalyst in real feed at industrial conditions.  相似文献   

16.
The relationship between the activity and surface molybdenum species of nitrided 12.5% MoO3/Al2O3 was studied in the hydrodenitrogenation (HDN) of carbazole at 573 K and 10.1 MPa total pressure. The surface molybdenum species were determined by the desorption of nitrogen gas during TPD. The surface area of NH3-cooled Mo/Al2O3 nitrided at 773 and 1173 K was decreased by 8% and 61% from 245 m2 g−1 of the fresh MoO3/Al2O3, respectively. The NH3-cooled Mo/Al2O3 catalysts had slightly higher surface area than the He-cooled catalysts. The HDN rate increased with increasing nitriding temperature in the HDN of carbazole on the nitride catalysts. The NH3-cooled Mo/Al2O3 catalysts nitrided at 1173 K were the most active in carbazole HDN and the He-cooled catalyst nitrided at 773 K was the least.  相似文献   

17.
采用溶胶-凝胶法制备了TiO2-Al2O3复合载体, 以柠檬酸(CA)为络合剂采用浸渍法制备了Ni2P负载的TiO2-Al2O3复合载体催化剂, 并用 X 射线衍射(XRD)、N2吸附比表面积(BET)测定技术对催化剂的结构和性质进行了表征, 考察了载体焙烧温度、催化剂焙烧温度、还原温度、还原压力对其进行的二苯并噻吩(DBT)加氢脱硫(HDS)性能的影响。结果表明, 升高载体焙烧温度有利于催化剂表面上活性物种的分散, 但焙烧温度过高会导致催化剂烧结, 适宜的载体焙烧温度为550℃。当还原温度为500~550℃时, 磷化镍主要以Ni12P5相形式存在, 且随着还原温度的升高, Ni12P5的衍射峰强度逐渐增强, 还原温度为700℃时, 可得到单一的Ni2P物相。载体焙烧温度为550℃, 催化剂焙烧温度为500℃, 还原温度为700℃, 常压还原制备的Ni2P/TiO2-Al2O3催化剂具有最好的活性。在360℃、3.0MPa、氢油体积比500、液时体积空速2.0h-1的条件下, 反应4h时, DBT转化率为99.5 %。  相似文献   

18.
The hydrodesulphurization (HDS) of thiophene at atmospheric pressure, hydrodenitrogenation (HDN) of 2,6 diethylaniline (DEA) and of 1,2,3,4 tetrahydroquinoline (THQ) at 70 atm in a dynamic flow microreactor - these molecules being present alone or mixed in the feed - and finally HDN of mixtures of quinoline (Q) at 70 atm or of phenanthridine (Ph) at 140 atm with DEA in a batch reactor were the test reactions used to compare the performances of (Ni)---Mo---S catalysts supported on MgAl2O4 and NiAl2O4 with a classical Ni---Mo---S/γ Al2O3 commercial catalyst. Some of the catalysts supported on NiAl2O4 appeared to be superior to the commercial one, whereas those supported on MgAl2O4 were found to be less active. HDS of thiophene, as well as the amount of carbon monoxide adsorbed at 0°C by sulphided catalysts permitted the prediction of the order of HDN activity of the catalysts for the conversion of some nitrogen-containing molecules. A strong inhibiting effect of molecules like Q, THQ or Ph (or some of their products formed during the process) on the HDN of DEA has been found and attributed to the competitive adsorption of these molecules on the supported active phase.  相似文献   

19.
Ethanol steam reforming was studied over Ni/Al2O3 catalysts. The effect of support (- and γ-Al2O3), metal loading and a comparison between conventional H2 reduction with an activation method employing a CH4/O2 mixture was investigated. The properties of catalysts were studied by N2 physisorption, X-ray diffraction (XRD) and temperature programmed reduction (TPR). After activity tests, the catalysts were analyzed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG/DTA). Ni supported on γ-Al2O3 was more active for H2 production than the catalyst supported on -Al2O3. Metal loading did not affect the catalytic performance. The alternative activation method with CH4/O2 mixture affected differently the activity and stability of the Ni/γ-Al2O3 and the Ni/-Al2O3 catalyst. This activation method increased significantly the stability of Ni/-Al2O3 compared to H2 reduction. SEM and TG/DTA analysis indicate the formation of filamentous carbon during the CH4/O2 activation step, which is associated with the increasing catalyst activity and stability. The effect of temperature on the type of carbon formed was investigated; indicating that filamentous coke increased activity while encapsulating coke promoted deactivation. A discussion about carbon formation and the influence on the activity is presented.  相似文献   

20.
MoNi/Al2O3 catalysts have been widely used for hydrodesulphurisation of oil fractions. In order to enhance the catalytic activities for HDS and HDN, catalysts supported on titania-modified alumina carriers have been studied. The MoNi/Al2O3–TiO2catalysts were characterised by benzene sorption, ammonia sorption, temperature programmed reduction, X-ray diffraction and scanning electron microscopy. The supports effect was examined by comparing thiophene conversion and sulphur or nitrogen contents in diesel oil fraction.  相似文献   

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