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1.
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
2.
The influence of the addition of 1–10 vol.% of hydrogen or carbon dioxide to the feed during the partial oxidation of methane was studied over a NiO/γ-Al 2O 3 catalyst. The addition of H 2 decreases the conversion and syngas selectivity. This decrease of performance seems to be related to a higher reduction of the catalyst due to the H 2 co-feeding. The addition of CO 2 also appears unfavorable to the production of hydrogen but increases the CO yield. A combination of the dry reforming and the reverse water gas shift reactions is suggested to explain the observed modifications in the product yields. 相似文献
3.
This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO 2 with C 2H 4 as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C 2H 4/SO 2, and pretreatment are all important factors affecting catalyst activity. Fe 2O 3/γ-Al 2O 3 was found to be the most active catalyst among six γ-Al 2O 3-supported metal oxide catalysts tested. With Fe 2O 3 as the active species, of the supports tested, CeO 2 is the most suitable one. Using this Fe 2O 3/CeO 2 catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C 2H 4/SO 2 is 1:1, and the catalyst presulfidized by H 2+H 2S exhibits a higher performance than those pretreated with H 2 or He. Although the feed concentrations of C 2H 4:SO 2 being 3000:3000 ppm provide a higher conversion of SO 2, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C 2H 4 temperature-programmed desorption (C 2H 4-TPD) and SO 2-TPD desorption patterns illustrate that Fe 2O 3/CeO 2 can adsorb and desorb C 2H 4 and SO 2 more easily than can Fe 2O 3/γ-Al 2O 3. Moreover, the SO 2-TPD patterns further show that Fe 2O 3/γ-Al 2O 3 is more seriously inhibited by SO 2. These findings may properly explain why Fe 2O 3/CeO 2 has a higher activity for the reduction of SO 2. 相似文献
4.
Mn effect and characterization on γ-Al 2O 3-, -Al 2O 3- and SiO 2-supported Ru catalysts were investigated for Fischer–Tropsch synthesis under pressurized conditions. In the slurry phase Fischer–Tropsch reaction, γ-Al 2O 3 catalysts showed higher performance on CO conversion and C 5+ selectivity than -Al 2O 3 and SiO 2 catalysts. Moreover, Ru/Mn/γ-Al 2O 3 exhibited high resistance to catalyst deactivation and other catalysts were deactivated during the reaction. From characterization results on XRD, TPR, TEM, XPS and pore distribution, Ru particles were clearly observed over the catalysts, and γ-Al 2O 3 catalysts showed a moderate pore and particle size such as 8 nm, where -Al 2O 3 and SiO 2 showed highly dispersed ruthenium particles. The addition of Mn to γ-Al 2O 3 enhanced the removal of chloride from RuCl 3, which can lead to the formation of metallic Ru with moderate particle size, which would be an active site for Fischer–Tropsch reaction. Concomitantly, manganese chloride is formed. These schemes can be assigned to the stable nature of Ru/Mn/γ-Al 2O 3 catalyst. 相似文献
5.
通过制备高纯度的前驱体湃铝石获得了η-Al 2O 3材料,采用XRD验证了η-Al 2O 3与γ-Al 2O 3在晶相结构上的差异,比较了两者的表面形貌、织构及酸碱性能,结果显示,η-Al 2O 3与γ-Al 2O 3的比表面积相当,但η-Al 2O 3具有更弱的弱碱位和较少的强碱位,并拥有丰富的中等强度酸性位。将η-Al 2O 3与γ-Al 2O 3作为催化剂应用于CS 2水解反应,结果表明,在(200~450) ℃测试温度范围内,η-Al 2O 3催化剂对CS 2的水解活性始终优于γ-Al 2O 3,两种催化剂上CS 2反应的浓度效应也明显不同,推测与它们的酸碱性质影响了对CS 2的吸附能力有关,导致两者催化CS 2水解反应遵循了不同的机制。 相似文献
6.
The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al 2O 3 catalysts on the surface properties and reactivity for NO reduction by C 3H 6 in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al 2O 3 catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al 2O 3 and 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalysts calcined at 1073 K possess a CuAl 2O 4 phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C 3H 6 shows that the CuAl 2O 4 is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K, although these catalysts possess the same CuAl 2O 4 phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al 2O 3 catalyst calcined at 1073 K is attributed to the formation of less active CuAl 2O 4 phase with high aggregation and preferential promotion of C 3H 6 combustion to CO x by MnO 2. The engine dynamometer test for NO reduction shows that the C 3H 6 is a more effective reducing agent for NO reduction than the C 2H 5OH. The maximum reactivity for NO reduction by C 3H 6 is reached when the NO/C 3H 6 ratio is one. 相似文献
7.
Reforming of methane with carbon dioxide into syngas over Ni/γ-Al 2O 3 catalysts modified by potassium, MnO and CeO 2 was studied. The catalysts were prepared by impregnation technique and were characterized by N 2 adsorption/desorption isotherm, BET surface area, pore volume, and BJH pore size distribution measurements, and by X-ray diffraction and scanning electron microscopy. The performance of these catalysts was evaluated by conducting the reforming reaction in a fixed bed reactor. The coke content of the catalysts was determined by oxidation conducted in a thermo-gravimetric analyzer. Incorporation of potassium and CeO 2 (or MnO) onto the catalyst significantly reduced the coke formation without significantly affecting the methane conversion and hydrogen yield. The stability and the lower amount of coking on promoted catalysts were attributed to partial coverage of the surface of nickel by patches of promoters and to their increased CO 2 adsorption, forming a surface reactive carbonate species. Addition of CeO 2 or MnO reduced the particle size of nickel, thus increasing Ni dispersion. For Ni–K/CeO 2–Al 2O 3 catalysts, the improved stability was further attributed to the oxidative properties of CeO 2. Results of the investigation suggest that stable Ni/Al 2O 3 catalysts for the carbon dioxide reforming of methane can be prepared by addition of both potassium and CeO 2 (or MnO) as promoters. 相似文献
8.
Two types of NiO/γ-Al 2O 3 catalysts prepared by the impregnation and the sol–gel method were used for the partial oxidation of methane to syngas at 850°C (GHSV1.8×10 5 lkg −1 h −1). The effects of the carbon deposition, the loss and sintering of nickel and the phase transformation of γ-Al 2O 3 support on the catalytic performance during 80 h POM reaction were investigated with a series of characterization such as XRD, BET, AAS, TG, and XPS. The results indicated that the carbon deposition and the loss and sintering of nickel could not cause the serious decrease of catalytic performance over NiO/γ-Al 2O 3 catalyst during the short-time reaction. However, the slow process of the support γ-Al 2O 3 phase transforming into -Al 2O 3 could slowly decrease the performance of NiO/γ-Al 2O 3 catalysts. Aimed at the reasons of the deactivation, an improved catalyst was obtained by the complexing agent-assisted sol–gel method. 相似文献
9.
Ni catalysts supported on γ-Al 2O 3, CeO 2 and CeO 2–Al 2O 3 systems were tested for catalytic CO 2 reforming of methane into synthesis gas. Ni/CeO 2–Al 2O 3 catalysts showed much better catalytic performance than either CeO 2- or γ-Al 2O 3-supported Ni catalysts. CeO 2 as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO 2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al 2O 3 catalysts for this reaction. A weight loading of 1–5 wt% CeO 2 was found to be the optimum. Ni catalysts with CeO 2 promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO 2-promoted catalysts are attributed to the oxidative properties of CeO 2. 相似文献
10.
Dispersing La 2O 3 on δ- or γ-Al 2O 3 significantly enhances the rate of NO reduction by CH 4 in 1% O 2, compared to unsupported La 2O 3. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La 2O 3 precursor used, the pretreatment, and the La 2O 3 loading. The most active family of catalysts consisted of La 2O 3 on γ-Al 2O 3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m 2) occurred between the addition of one and two theoretical monolayers of La 2O 3 on the γ-Al 2O 3 surface. The best catalyst, 40% La 2O 3/γ-Al 2O 3, had a turnover frequency at 700°C of 0.05 s −1, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La 2O 3/Al 2O 3 catalysts exhibited stable activity under high conversion conditions as well as high CH 4 selectivity (CH 4 + NO vs. CH 4 + O 2). The addition of Sr to a 20% La 2O 3/γ-Al 2O 3 sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO =4 to the latter Sr-promoted La 2O 3/Al 2O 3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La 2O 3. Dispersing La 2O 3 on SiO 2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La 2O 3. This is presumably due to water sensitivity and silicate formation. The La 2O 3/Al 2O 3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications. 相似文献
11.
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
12.
通过等体积浸渍法制备单贵金属Pt/γ-Al 2O 3和双金属Pt-Ce/γ-Al 2O 3催化剂,考察Ce对催化剂活性的影响,确定催化剂最优配比。结果表明,当Pt的负载量为质量分数0.5%时,Pt/γ-Al 2O 3催化活性最高;当Pt的负载量为质量分数0.2%,Ce的负载量为质量分数1.0%时,Pt-Ce/γ-Al 2O 3催化剂的催化活性最高。Pt-Ce/γ-Al 2O 3催化剂的甲苯转化率高于Pt/γ-Al 2O 3催化剂。随着Pt负载量增大,催化剂孔容、孔径减小。粉体式催化剂性能优于整体式催化剂,但差别不大;Ce的添加有助于催化剂活性的提升。 相似文献
13.
Methane conversion to C 2 hydrocarbons and hydrogen has been investigated in a needle-to-plate reactor by pulsed streamer and pulsed spark discharges and in a wire-to-cylinder dielectric barrier discharge (DBD) reactor by pulsed DC DBD and AC DBD at atmospheric pressure and ambient temperature. In the former two electric discharge processes, acetylene is the dominating C 2 products. Pulsed spark discharges gives the highest acetylene yield (54%) and H 2 yield (51%) with 69% of methane conversion in a pure methane system and at 10 SCCM of flow rate and 12 W of discharge power. In the two DBD processes, ethane is the major C 2 products and pulsed DC DBD provides the highest ethane yield. Of the four electric discharge techniques, ethylene yield is less than 2%. Energy costs for methane conversion, acetylene or ethane (for DBD processes) formation, and H 2 formation increase with methane conversion percentage, and were found to be: in pulsed spark discharges (methane conversion 18–69%), 14–25, 35–65 and 10–17 eV/molecule; in pulsed streamer discharges (methane conversion 19–41%), 17–21, 38–59, and 12–19 eV/molecule; in pulsed DBD (methane conversion 6–13%), 38–57, 137–227 and 47–75 eV/molecule; in AC DBD (methane conversion 5–8%), 116–175, 446–637, and 151–205 eV/molecule, respectively. The immersion of the γ-Al 2O 3 pellets in the pulsed streamer discharges, or in the pulsed DC DBD, or in the AC DBD has a positive effect on increasing methane conversion and C 2 yield. 相似文献
14.
以γ-Al 2O 3为载体,采用等体积分步浸渍法制备了以Ni为活性组分,La、Ce、Fe、Cr、Co为助剂的催化剂M/γ-Al 2O 3,在固定床管式反应器中研究了M/γ-Al 2O 3催化剂的性能,考察了反应温度、水碳比和空速对氢产率的影响,并对催化剂进行XRD、SEM和BET表征。结果表明,NiLaCeFeCrCo/γ-Al 2O 3催化剂具有较好的催化性能,在反应温度700 ℃、水碳物质的量比10和空速6 min -1的条件下,氢产率达到27.335 mol·mol -1,并在300 min内表现出较好的活性,平均氢产率为21.966 mol·mol -1。 相似文献
15.
The effectiveness of Ag/Al 2O 3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al 2O 3, and Al(OH) 3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O 2, NO + O 2-temperature programmed desorption (TPD), H 2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C 3H 6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C 3H 6 conversion was achieved over Ag/Al 2O 3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al 2O 3 (I) is deemed to be crucial for NO selective reduction into N 2. By contrast, a high C 3H 6 conversion simultaneously with a moderate N 2 yield was observed over Ag/Al 2O 3 (II) prepared from a γ-Al 2O 3 source. The larger particles of Ag mO ( m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al 2O 3 (III) was obtained via employing a Al(OH) 3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al 2O 3 (I). A subsequent calcination of Ag/Al 2O 3 (III) at 800 °C led to the generation of Ag/Al 2O 3 (IV) catalyst yielding a significant enhancement in both N 2 yield and C 3H 6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al 2O 3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al 2O 3 (II and V) > Ag/Al 2O 3 (IV) > Ag/Al 2O 3 (I) > Ag/Al 2O 3 (III) and Al 2O 3 (I). The formation of nitrate species is an important step for the deNO x process, which can be promoted by increasing O 2 feed concentration as evidenced by NO + O 2-TPD study for Ag/Al 2O 3 (I), achieving a better catalytic performance. 相似文献
16.
Wood-derived bio-oil contains high amounts of compounds with different oxygen-containing functional groups that must be removed to improve the fuel characteristics. Elimination of oxygen from carboxylic groups was studied with model compounds, methyl heptanoate and methyl hexanoate, on sulphided NiMo/γ-Al 2O 3 and CoMo/γ-Al 2O 3 catalysts in a flow reactor. Catalyst performances and reaction schemes were addressed. Aliphatic methyl esters produced hydrocarbons via three main paths: The first path gave alcohols followed by dehydration to hydrocarbons. Deesterification yielded an alcohol and a carboxylic acid in the second path. Carboxylic acid was further converted to hydrocarbons either directly or with an alcohol intermediate. Decarboxylation of the esters led to hydrocarbons in the third path. No oxygen-containing compounds were detected at complete conversions. However, the product distributions changed with time, even at complete conversions, indicating that both catalysts deactivated under the studied conditions. 相似文献
17.
The interactions NO—CO and O 2—NO—CO have been studied onCuCo 2O 4γ-Al 2O 3 and on γ-Al 2O 3- and CuCo 2O 4γ-Al 2O 3-supported Pt, Rh and Pt—Rh catalysts. The deposition of noble metals (Pt, Rh and Pt—Rh) on CuCo 2O 4γ-Al 2O 3 instead of γ-Al 2O 3 is beneficial in: lowering the temperature at which maximum N 2O is formed and decreasing the maximum N 2O concentration attained; lowering the onset temperature of NO to N 2 reduction, and increasing the N 2 selectivity; preserving the activity towards NO to N 2 reduction on a higher level following the concentration step NO + COO 2+ NO + CO and changing the conditions from stoichiometric to oxidizing (50% excess of oxidants). The reason for this behaviour of the CuCo 2O 4γ-Al 2O 3-based noble metal catalysts is the formation (reversible) of a reduced surface layer on the CuCo 2O 4 supported spinel under the conditions of a stoichiometric NO + CO mixture. 相似文献
18.
The role of ozone was studied for two different configurations combining non-thermal plasma (NTP) and heterogeneous catalysis, namely the use of a gas phase plasma with subsequent exposure of the effluent to a catalyst in a packed-bed reactor (post-plasma treatment) and the placement of the catalyst directly in the discharge zone (in-plasma catalysis). Non-porous and porous alumina and silica were deployed as model catalysts. The oxidation of immobilised hydrocarbons, toluene as a volatile organic compound and CO as an inorganic pollutant were studied in both operational modes. While conversion and selectivity of hydrocarbon oxidation in the case of catalytic post-plasma treatment can be fully explained by the catalytic decomposition of O3 on γ-Al2O3, the conversion processes for in-plasma catalysis are more complex and significant oxidation was also measured for the other three materials (-Al2O3, quartz and silica gel). It became obvious that additional synergetic effects can be utilised in the case of in-plasma catalysis due to short-lived species formed in the NTP. The capability of porous alumina for ozone decomposition was found to be correlated with its activity for oxidation of carbon-containing agents. It could be clearly shown that the reaction product CO2 poisons the catalytic sites at the γ-Al2O3 surface. The catalytic activity for O3 decomposition can be partially re-established by NTP treatment. However, for practical purposes the additional reaction pathways provided by in-plasma catalytic processes are essential for satisfactory conversion and selectivity. 相似文献
19.
The influence of the addition of 5 vol.% of carbon monoxide, hydrogen, carbon dioxide or water to the feed of partial oxidation of methane was investigated over Ni/γ-Al 2O 3 and Rh/γ-Al 2O 3 catalysts. In addition to catalytic tests, thermodynamic calculations were performed to predict the effect of these gas co-feeds. Compared to the thermodynamic trends, differences in the influence of the co-feeding on catalytic performances were observed between both catalysts. Co-feeding of CO, H 2, CO 2 or H 2O can modify the oxidation state and dispersion of the metal component of the catalysts during reaction, and as a consequence, their performances. Changes in catalysts can be due to dynamic processes occurring during reaction. It is suggested to take these processes into account in a more complex kinetic equation for the reactions involved. 相似文献
20.
The effects of carbon dioxide on the dehydrogenation of C 3H 8 to produce C 3H 6 were investigated over several Cr 2O 3 catalysts supported on Al 2O 3, active carbon and SiO 2. Carbon dioxide exerted promoting effects only on SiO 2-supported Cr 2O 3 catalysts. The promoting effects of carbon dioxide over a Cr 2O 3/SiO 2 catalyst were to enhance the yield of C 3H 6 and to suppress the catalyst deactivation. 相似文献
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