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1.
D. Ferdous  J. Adjaye 《Fuel》2006,85(9):1286-1297
A detailed experimental study was performed in a trickle-bed reactor using bitumen derived gas oil. The objective of this work was to compare the activity of NiMo/Al2O3 catalyst containing boron or phosphorus for the hydrotreating and mild hydrocracking of bitumen derived gas oil. Experiments were performed at the temperature and LHSV of 340-420 °C and 0.5-2 h−1, respectively, using NiMo/Al2O3 catalysts containing 1.7 wt% boron or 2.7 wt% phosphorus. In the temperature range of 340-390 °C, higher nitrogen conversion was observed from boron containing catalyst than that from phosphorus containing catalyst whereas in the same temperature range, phosphorus containing catalyst gave higher relative removal of sulfur than boron containing catalyst. Phosphorus containing catalyst showed excellent hydrocracking and mild hydrocracking activities at all operating conditions. Higher naphtha yield and selectivity were obtained using phosphorus containing catalyst at all operating conditions. Maximum gasoline selectivity of ∼45 wt% was obtained at the temperature, pressure, and LHSV of 400 °C, 9.4 MPa and 0.5 h−1, respectively, using catalyst containing 2.7 wt% phosphorus.  相似文献   

2.
The effect of two binder systems — a silica-based system and a silica–kaolin–clay–phosphate-based system — on a doubly promoted Fischer–Tropsch (FT) synthesis iron catalyst (100Fe/5Cu/4.2K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and spray drying at 270°C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt.%. A catalyst with 12 wt.% binder silica was found to have the highest attrition resistance. The FT activity and selectivity of this catalyst are better than a Ruhrchemie catalyst at 270°C and 1.48 MPa. The addition of precipitated silica or kaolin to catalysts containing 10–12 wt.% binder silica decreases attrition resistance and increases methane selectivity. Based on the experience gained, a catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95% CO conversion over 125 h of testing at 270°C, 1.48 MPa, and 2 NL/g-cat/h and had less than 4% methane selectivity. Its attrition resistance was one of the highest among the catalysts tested.  相似文献   

3.
The CO conversion and selectivity to C1+ and C11+ wax products over Co/Al2O3 as well as Ru/Co/Al2O3 Fischer-Tropsch (F-T)catalysts were investigated by varying reaction temperature (210-250 °C), system pressure (1.0-3.0 MPa), GHSV (1000-6000 L/kg/h), superficial gas velocity (1.7-13.6 cm/s) and slurry concentration (9.09-26.67 wt.%) in a slurry bubble column reactor (0.05 m diameter × 1.5 m height) to determine the optimum operating conditions. Squalane or paraffin wax was used as initial liquid media. The overall CO conversion increased with increasing reaction temperature, system pressure and catalyst concentration. However, the local maximum CO conversion was exhibited at GHSV of 1500-2000 L/kg/h and superficial gas velocity of 3.4-5.0 cm/s. The CO conversion in the case of Ru/Co/Al2O3 was much higher and stable than that in the case of Co/Al2O3. The selectivity to C11+ wax products increased slightly with increasing GHSV; on the other hand, it decreased with increasing reaction temperature, system pressure, and solid concentration in a slurry bubble column reactor. It could be concluded that the optimum operating conditions based on the yield of hydrocarbons and wax products were; UG = 6.8-10 cm/s, Cs = 15 wt.%, T = 220-230 °C, P = 2.0 MPa in a slurry bubble column reactor for F-T synthesis.  相似文献   

4.
A user-friendly simulator based on a comprehensive computer model for slurry bubble column reactors (SBCRs) for Fischer-Tropsch (F-T) synthesis, taking into account the hydrodynamics, kinetics, heat transfer, and mass transfer was developed. The hydrodynamic and mass transfer data obtained in our laboratories under typical F-T conditions along with those available in the literature were correlated using Back Propagation Neural Network and empirical correlations with high confidence levels. The data used covered wide ranges of reactor geometry, gas distributor, and operating conditions. All reactor partial differential equations, equation parameters and boundary conditions were simultaneously solved numerically.The simulator was systematically used to predict the effects of reactor geometry (inside diameter and height) as well as superficial gas velocity and catalyst concentration on the performance of a large-scale SBCR provided with cooling pipes and operating under F-T conditions with cobalt-supported catalyst and H2/CO = 2. The performance of the SBCR was expressed in terms of CO conversion, liquid hydrocarbon yield, catalyst productivity, and space time yield. The simulator was also used to optimize the reactor geometry and operating conditions in order to produce 10,000 barrels/day (bbl/day) of liquid hydrocarbons.  相似文献   

5.
Ni modified K2CO3/MoS2 catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H2/CO (molar radio) = 2.0, GHSV = 3000 h 1, and P = 10.0 MPa. Compared with conventional K2CO3/MoS2 catalyst, Ni/K2CO3/MoS2 catalyst showed higher activity and higher selectivity to C2+OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K2CO3/MoS2 was higher, however, it was close to that of K2CO3/MoS2 catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K2CO3/MoS2 catalyst.  相似文献   

6.
A cross-shaped pattern was formed on the surface of Ba0.5Sr0.5Co0.8Fe0.2O3 − δ oxygen permeation membrane by laser ablation. A membrane reactor made from this membrane was operated for partial oxidation of methane to syngas in the presence of Ni/ZrO2 catalyst. The CH4 conversion and CO selectivity of the membrane reactor were 98.8% and 91.5%, respectively, and the oxygen permeation flux through the membrane was 11.0 ml/cm2 min at 850 °C. The effects of space velocity (SV) on CH4 conversion and CO selectivity in such reactor were discussed. The mechanism of POM in such membrane reactor may follow the combustion and reforming mechanism.  相似文献   

7.
The effect of vanadium promotion on activated carbon (AC)-supported cobalt catalysts in Fischer–Tropsch synthesis has been studied by means of XRD, TPR, CO-TPD, H2-TPSR of chemisorbed CO and F-T reaction. It was found that the CO conversion could be significantly increased from 38.9 to 87.4% when 4 wt.% V was added into Co/AC catalyst. Small amount of vanadium promoter could improve the selectivity toward C10–C20 fraction and suppress the formation of light hydrocarbon. The results of CO-TPD and H2-TPSR of adsorbed CO showed that the addition of vanadium increased the concentration of surface-active carbon species by enhancing CO dissociation and further improved the selectivity of long chain hydrocarbons. However, excess of vanadium increased methane selectivity and decreased C5+ selectivity.  相似文献   

8.
F.Y.A. El Kady  S. Shaban 《Fuel》2010,89(11):3193-36
CoMo/γ-Al2O3 catalyst containing 16.0 wt% MoO3 and 3.2 wt% CoO was prepared by equilibrium deposition filtration method (EDF). The CoMo oxidic catalyst was characterized by elemental analysis, N2 adsorption, XRD, and TPR. The sulfided catalyst was characterized by FTIR of adsorbed CO at 30 °C. Hydrodesulfurization (HDS) and hydrodearomatization activities were evaluated for heavy gas oil (HGO) in a trickle bed reaction system using the following conditions: reaction temperatures of 340, 360, 380 and 400 °C, a reaction pressure of 20, 35, 50 and 65 bar, a liquid hourly space velocity (LHSV) of 1.0, 1.5, 2.0, 2.5 and 3 h−1 and a H2/feed ratio of 400 L L−1. The experimental results were used to determine apparent reaction orders and activation energies. The dispersion, nature of active sites and hydrotreating activity of this catalyst were compared with the conventionally prepared CoMo/γ-Al2O3 catalyst containing similar wt% of MoO3 and CoO. The CoMo catalyst prepared by equilibrium deposition filtration method has higher HDS and HDA rate constants than the conventional catalyst due to an improved dispersion of MoS2.  相似文献   

9.
Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3−δ packed with Ni-based catalyst had high oxygen permeability and could be used for syngas production by partial oxidation of methane in coke oven gas (COG). The BCFNO membrane itself had a poor catalytic activity to partial oxidation of CH4 in COG. After the catalyst was packed on the membrane surface, 92% of methane conversion, 90% of H2 selectivity, 104% of CO selectivity and as high as 15 ml/cm2/min of oxygen permeation flux were obtained at 1148 K. During continuously operating for 550 h at 1148 K, no degradation of performance of the BCFNO membrane reactor was observed under the condition of hydrogen-rich COG. The possible reaction pathways were proposed to be an oxidation-reforming process. The oxidation of H2 in COG with the surface oxygen on the permeation side improves the oxygen flux through the membrane, and H2O reacts with CH4 by reforming reactions to form H2 and CO.  相似文献   

10.
The effect of CO conversion on hydrocarbon selectivities (i.e., CH4, C5+, olefin and paraffin), H2/CO usage ratios, CO2 selectivity, and catalyst stability over a wide range of CO conversion (12?C94%) on 0.27%Ru?C25%Co/Al2O3 catalyst was studied under the conditions of 220 °C, 1.5 MPa, H2/CO feed ratio of 2.1 and gas space velocities of 0.3?C15 NL/g-cat/h in a 1-L continuously stirred tank reactor (CSTR). Catalyst samples were withdrawn from the CSTR at different CO conversion levels, and Co phases (Co, CoO) in the slurry samples were characterized by XANES, and in the case of the fresh catalysts, EXAFS as well. Ru was responsible for increasing the extent of Co reduction, thus boosting the active site density. At 1%Ru loading, EXAFS indicates that coordination of Ru at the atomic level was virtually solely with Co. It was found that the selectivities to CH4, C5+, and CO2 on the Co catalyst are functions of CO conversion. At high CO conversions, i.e. above 80%, CH4 selectivity experienced a change in the trend, and began to increase, and CO2 selectivity experienced a rapid increase. H2/CO usage ratio and olefin content were found to decrease with increasing CO conversion in the range of 12?C94%. The observed results are consistent with water reoxidation of Co during FTS at high conversion. XANES spectroscopy of used catalyst samples displayed spectra consistent with the presence of more CoO at higher CO conversion levels.  相似文献   

11.
The use of an iron dispersed catalyst, derived from Fe3(CO)12, for extra-heavy crude oil upgrading using methane as source of hydrogen was studied. The upgrading reactions were carried out batchwise in a stainless-steel 300 ml Parr reactor with 250 ppm of Fe at a temperature of 410-420 °C, a pressure of 11 MPa of CH4, and a residence time of 1 h. In the presence of Fe3(CO)12, the reaction of Hamaca extra-heavy crude oil led to a reduction of two orders of magnitude in the viscosity (from 500 to 1.3 Pa s), 14% reduction in sulfur content, and 41% conversion of the >500 °C fraction in the upgraded product with respect to the original crude. The iron catalyst was isolated from the coke produced from the upgrading reaction and was analyzed by XPS, EDAX, and Mössbauer spectroscopy. The results indicated the presence of a Fe-V mixed sulfide species with a composition ca. (Fe0.6V0.4)zS, where z is in the range 0.8-0.9.  相似文献   

12.
Fischer-Tropsch synthesis (FTS) was carried out in a fixed bed reactor with a highly effective cobalt catalyst for wax production. The procedure for reducing the inactive cobalt oxide to the active cobalt catalyst was examined by X-ray diffraction (XRD) and temperature-programmed reduction (TPR). The results showed that 300 ml/min H2 at 350 °C for 16 h was suitable for reducing the inactive Co oxides to active metallic Co sites. In the case of the powder and pellet type cobalt catalysts with a reactant (H2/CO = 2:1) flow rate of 15 gcat min L−1, catalyst deactivation occurred as a result of mass transfer limitations of the hydrocarbon and water produced on the catalyst. On the other hand, the pellet type cobalt catalyst with a reactant flow rate of 45 gcat min L−1 showed activity not only for liquid hydrocarbon (C5+) formation but also for gas product (CH4 and CO2) formation. In particular, the methane yield reached almost 20% due to heat transfer limitation in the catalyst. Considering the heat and mass transfer limitations in the cobalt catalyst, a Co-foam catalyst with an inner metallic foam frame and an outer cobalt catalyst was developed. SEM-EDS Co-mapping revealed the cobalt atoms to be distributed equally over the surface of the Co-foam catalyst. The Co-foam catalyst was highly selective toward liquid hydrocarbon production and the liquid hydrocarbon productivity at 203 °C was 52.5 ml  h−1, which was higher than that by the Co-pellet. In addition, the chain length probability, α, by the Co-foam catalyst was 0.923 and wax formation was especially favored.  相似文献   

13.
CuO-CoO-Cr2O3 mixed with MFI Zeolite (Si/Al = 35) prepared by co-precipitation was used for synthesis gas conversion to long chain hydrocarbon fuel. CuO-CoO-Cr2O3 catalyst was prepared by co-precipitation method using citric acid as complexant with physicochemical characterization by BET, TPR, TGA, XRD, H2-chemisorptions, SEM and TEM techniques. The conversion experiments were carried out in a fixed bed reactor, with different temperatures (225-325 °C), gas hourly space velocity (457 to 850 h−1) and pressure (28-38 atm). The key products of the reaction were analyzed by gas chromatography mass spectroscopy (GC-MS). Significantly high yields of liquid aromatic hydrocarbon products were obtained over this catalyst. Higher temperature and pressure favored the CO conversion and formation of these liquid (C5-C15) hydrocarbons. Higher selectivity of C5 + hydrocarbons observed at lower H2/CO ratio and GHSV of the feed gas. On the other hand high yields of methane resulted, with a decrease in C5+ to C11+ fractions at lower GHSV. Addition of MFI Zeolite (Si/Al = 35) to catalyst CuO-CoO-Cr2O3 resulted a high conversion of CO-hydrogenation, which may be due to its large surface area and small particle size creating more active sites. The homogeneity of various components was also helpful to enhance the synergistic effect of Co promoters.  相似文献   

14.
The K2CO3/MoS2 catalyst for higher alcohols synthesis with synthesis gas as feedstock was prepared. The catalyst was characterized by TPR, in-situ XPS, XRD and SEM. Effects of pretreatment with H2, CO or synthesis gas on activity and selectivity of the catalyst were investigated. Results showed that there was a remarkable induction period about 180 h at the initial reaction stage for the un-treated catalyst. The catalytic performances for alcohols synthesis changed notably during the induction period. The induction period was confirmed to be resulted primarily from the sulfur losing and K element dispersion on the surface of ADM catalysts. Pretreatment of the catalyst could remarkably shorten the time of induction period as well as promote the catalytic activity. Furthermore, the higher alcohols (C2 + OH) content in the liquid products were enhanced after the catalyst pretreated by CO or synthesis gas which could be ascribed to the increasing of Mo4+ content on the surface of the catalyst.  相似文献   

15.
Yuying Shu 《Carbon》2005,43(7):1517-1532
A series of nickel, molybdenum, and tungsten metal phosphides deposited on a carbon black support (Ni2P/C, MoP/C, and WP/C) were synthesized by means of temperature-programmed reduction. The samples were characterized by BET surface area, CO uptake, X-ray diffraction (XRD), elemental analysis, and extended X-ray absorption fine structure (EXAFS) measurements. The activity of these catalysts was measured at 613 K and 3.1 MPa in a three-phase, packed-bed reactor for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) with a model liquid feed containing 500 ppm sulfur as 4,6-dimethyldibenzothiophene (4,6-DMDBT), 3000 ppm sulfur as dimethyl disulfide, and 200 ppm nitrogen as quinoline. The Ni2P/C catalyst was found to exhibit the best hydroprocessing performance based on equal CO chemisorption sites (70 μmol) loaded in the reactor. An optimum Ni loading for HDS and HDN activity was found as 1.656 mmol g−1 (11.0 wt.% Ni2P) which gave an HDS conversion of 99% and an HDN conversion of 100% at a molar space velocity of 0.88 h−1. These were much higher than those of a commercial Ni-Mo-S/γ-Al2O3 catalyst which gave an HDS conversion of 68% and an HDN conversion of 94%, and a previously reported best Ni2P/SiO2 catalyst which gave an HDS conversion of 76% and an HDN conversion of 92%. The use of carbon instead of silica as a support gave rise to other differences, which included smaller particle size, higher CO uptake, lessened retention of P on the support, and reduced sulfur deposition. The stability of the 11.0 wt.% Ni2P/C catalyst was also excellent with no deactivation observed over 110 h of time on stream. The activity and stability of the Ni2P/C catalyst were affected by the phosphorous content, both reaching a maximum with an initial Ni/P ratio of 1/2. EXAFS and elemental analysis of the spent samples indicated the formation of a surface phosphosulfide phase on the Ni2P, which was beneficial for hydrotreating activity, while the bulk structure of the phosphides was maintained during the course of reaction as revealed from the XRD patterns.  相似文献   

16.
An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNTs)-supported bimetallic cobalt/iron catalysts is reported. Up to 4 wt.% of iron is added to the 10 wt.% Co/CNT catalyst by co-impregnation. The physico-chemical properties, FTS activity and selectivity of the bimetallic catalysts were analyzed and compared with those of 10 wt.% monometallic cobalt and iron catalysts at similar operating conditions (H2/CO = 2:1 molar ratio, P = 2 MPa and T = 220 °C). The metal particles were distributed inside the tubes and the rest on the outer surface of the CNTs. For iron loadings higher than 2 wt.%, Co–Fe alloy was revealed by X-ray diffraction (XRD) techniques. 0.5 wt.% of Fe enhanced the reducibility and dispersion of the cobalt catalyst by 19 and 32.8%, respectively. Among the catalysts studied, cobalt catalyst with 0.5% Fe showed the highest FTS reaction rate and percentage CO conversion. The monometallic iron catalyst showed the minimum FTS and maximum water–gas shift (WGS) rates. The monometallic cobalt catalyst exhibited high selectivity (85.1%) toward C5+ liquid hydrocarbons, while addition of small amounts of iron did not significantly change the product selectivity. Monometallic iron catalyst showed the lowest selectivity for 46.7% to C5+ hydrocarbons. The olefin to paraffin ratio in the FTS products increased with the addition of iron, and monometallic iron catalyst exhibited maximum olefin to paraffin ratio of 1.95. The bimetallic Co–Fe/CNT catalysts proved to be attractive in terms of alcohol formation. The introduction of 4 wt.% iron in the cobalt catalyst increased the alcohol selectivity from 2.3 to 26.3%. The Co–Fe alloys appear to be responsible for the high selectivity toward alcohol formation.  相似文献   

17.
Mass transfer limitations on fixed-bed for Fischer-Tropsch synthesis were investigated by changing synthesis gas superficial velocity, catalyst pellet size, and catalyst amount. To study external mass transfer limitation, synthesis gas superficial velocity was changed from 8.47 × 10− 4 m s− 1 to 3.39 × 10− 3 m s− 1. As a result, the synthesis gas superficial velocity of 3.39 × 10− 3 m s− 1 was most suitable for hydrocarbon chain growth resulting to liquid hydrocarbon formation. In case of internal mass transfer limitations, the effects of catalyst pellet size and catalyst amount (Wcat/F) were discussed. The large catalyst pellet showed higher C5+ selectivity and a lower α value compared to the small pellet because of more severe internal mass transfer limitations of α-olefin and long-chained hydrocarbons in the large pellet, respectively. Catalyst amount (Wcat/F) was inversely proportional to the internal mass transfer limitation because increased catalyst amount gave more time for liquid hydrocarbon products to diffuse from the catalyst pellet and, therefore, the catalyst amount of 4.5 g (Wcat/F = 45 gcat min L− 1) was most appropriate for liquid hydrocarbon formation.  相似文献   

18.
Cyclohexane, n-hexane, and isooctane were reacted with air in a Rh-monolith reactor and converted into synthesis gas (H2+CO) in yields exceeding 90%, with >95% conversion of fuels and 100% conversion of oxygen. The best catalyst was an 80 ppi washcoated alumina monolith containing 5 wt% Rh. There was a small effect of catalyst contact time on syngas selectivity and conversions for gas space velocities from 3×105 to 3×106 h–1. Preheating the feed enhances syngas selectivities slightly, but no reactor preheat is necessary provided the fuel remains vaporized. Addition of 25 mol% toluene to isooctane also produces syngas, olefins, and methane with 90% yield, including 70% yield to syngas. Partial oxidation of gasoline–air mixtures was attempted but the catalysts were poisoned after several hours, probably by sulfur and/or metals.  相似文献   

19.
Decomposition of NH3 to N2 with Fe and Ca catalysts supported on brown coal chars has been studied with a cylindrical quartz reactor from a viewpoint of hot gas cleanup. The catalyst is prepared by pyrolyzing a brown coal with Fe or Ca ions added. In the decomposition of 2000 ppm NH3 diluted with He at 750 °C and at a space velocity of 45,000 l/h, 2-6 wt% Fe catalysts are more active than not only 6 wt% Ca catalyst but also 8 wt% Fe catalyst loaded on a commercial activated carbon. The transmission electron microscope observations show that fine iron particles with the sizes of 20-50 nm account for the higher catalytic performances. When reaction temperature is increased to 850 °C, all of Fe and Ca catalysts on the chars achieve complete decomposition of NH3. The co-feeding of H2 with 2000 ppm NH3 improves the performance of the 2% Fe catalyst at 750 °C, but contrarily the coexistence of syngas (CO/H2=2) deactivates it remarkably, whereas the addition of CO2 to syngas restores the catalytic activity of the Fe to the original state without syngas. The powder X-ray diffraction and temperature programmed desorption measurements strongly suggest that the Fe and Ca catalysts promote NH3 decomposition through cycle mechanisms involving the formation of N-containing intermediate species and the subsequent decomposition to N2.  相似文献   

20.
M.K. van der Lee 《Carbon》2006,44(4):629-637
Carbon nanofibers (CNF) are non-microporous graphitic materials with a high surface area (100-200 m2/g), high purity and tunable surface chemistry. Therefore the material has a high potential for use as catalyst support. However, in some instances it is claimed that the low density and low mechanical strength of the macroscopic particles hamper their application. In this study we show that the bulk density and mechanical strength of CNF bodies can be tuned to values comparable to that of commercial fluid-bed and fixed-bed catalysts. The fibers were prepared by the chemical decomposition of CO/H2 over Ni/SiO2 catalysts. The resulting fibers bodies (1.2 μm) were replicates of the Ni/SiO2 bodies (0.5 μm) from which they were grown. The bulk density of CNF bodies crucially depended on the metal loading in the growth catalyst. Over 5 wt% Ni/SiO2 low density bodies (0.4 g/ml) are obtained while 20 wt% Ni/SiO2 leads to bulk densities up to 0.9 g/ml with a bulk crushing strength of 1.2 MPa. The 20 wt% catalysts grow fibers with diameters of ∼22 nm, which grow irregularly in space, resulting in a higher entanglement and a concomitant higher density and strength as compared to the thinner fibers (∼12 nm) grown from 5 wt% Ni/SiO2.  相似文献   

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