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1.
王奇  柯明  于沛  刘洋  张蕾  夏成杰  刘稳 《化工进展》2019,38(7):3163-3169
针对具有较高脱硫活性的CoMo/CeAl2O3催化剂,考察了Ce的不同浸渍方式对催化剂表面金属性质及催化活性的影响。结果表明,Ce采用不同浸渍方式(CoMo共浸渍)制备催化剂的加氢脱硫活性大小顺序为:先浸渍Ce后浸渍CoMo催化剂(CoMoCe/Al2O3)>先浸渍CoMo后浸渍Ce催化剂(CeCoMo/Al2O3)>Ce与载体混粘后浸渍CoMo催化剂(CoMo/CeAl2O3)。对于CoMoCe/Al2O3催化剂,先浸渍Ce减弱了二次浸渍CoMo时载体与Mo物种间的相互作用力,有利于Mo物种硫化,提高了硫化度,生成了较多的CoMoS活性相,增加了脱硫率;用实验室自组装固定床微型反应装置对CoMoCe/Al2O3催化剂进行了活性评价,以广西石化分公司(广西石化)重馏分油(≥65℃)为原料油时,产物硫含量可以降至8.6μg/g,RON损失1.3个单位。  相似文献   

2.
以中和法合成的不同SiO2含量的改性氧化铝为载体,本文制备系列Si改性的NiMo/Al2O3催化剂,采用X射线衍射(XRD)、N2物理吸附(BET)、程序升温脱附(NH3-TPD)、吡啶吸附红外光谱(Py-IR)、程序升温还原(H2-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   

3.
戴金鑫  刘晶  刘丰 《化工学报》2017,68(3):1163-1169
采用密度泛函理论方法研究H2S与NiFe2O4(001)完整表面和氧缺陷表面的相互作用机理。结果表明,H2S在NiFe2O4氧载体表面Ni原子位的吸附能比其在Fe原子位的吸附能大。氧缺陷的形成会使H2S在氧载体表面金属原子位的吸附能增大,并且Ni原子位吸附H2S的吸附能增加更为明显。因而,NiFe2O4氧载体表面的Ni原子位是H2S的主要吸附位。同时采用热力学方法进一步研究含H2S的合成气与NiFe2O4氧载体之间的反应,发现H2S与氧载体的反应产物与氧载体的还原程度密切相关。由于铁氧化物的深度还原过程受到热力学限制,H2S与NiFe2O4氧载体反应的主要产物为Ni3S2。密度泛函理论方法与热力学方法研究结果均表明H2S倾向于与NiFe2O4氧载体中Ni发生相互作用,这将对NiFe2O4氧载体的反应性能产生不利影响。  相似文献   

4.
本文通过溶液燃烧法,分别以Ni(CH3COO)2·4H2O、Ni(NO3)2·6H2O、NiCl2·6H2O和NiSO4·6H2O为镍源制备系列Ni/Al2O3催化剂,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、N2吸附-脱附、程序升温还原(H2-TPR)等表征手段,进一步揭示了镍源对合成Ni/Al2O3催化剂结构与其催化加氢性能间的构效关系的影响,结果表明,以Ni(CH3COO)2·4H2O为镍源制备的Ni/Al2O3催化剂比表面积最大,达到225m2·g-1,最大孔容0.39c...  相似文献   

5.
以Al2O3质量分数为10%的Al2O3-SiO2复合氧化物为载体,通过浸渍法制备一系列不同Ni负载量的Ni/Al2O3-SiO2催化剂。运用BET、XRD、H2-TPR和NH3-TPD-MS方法研究催化剂表面性质随活性金属Ni负载量的变化规律,探讨催化剂表面性质的变化对其顺酐加氢活性、选择性及催化剂稳定性的影响。结果表明,Ni/Al2O3-SiO2催化剂中的Ni质量分数由5.0%增加至12.5%时,γ-丁内酯收率由7.9%快速增至38.9%,进一步增加Ni质量分数至20.0%,γ-丁内酯收率增加趋于平缓。催化剂中Ni活性物种与催化剂酸性中心的数量是影响催化剂顺酐加氢活性的主要原因。  相似文献   

6.
孟凡会  常慧蓉  李忠 《化工学报》2014,65(8):2997-3003
采用共浸渍法制备了Ni-Mn/Al2O3催化剂,考察了助剂Mn的含量对催化剂结构及浆态床CO甲烷化性能的影响。采用XRD、H2-TPR、BET、TEM、H2-化学吸附等表征对催化剂进行了测试分析,结果表明,Mn助剂的引入能够促进Ni物种在载体表面的分散,减弱Ni物种与载体的相互作用,降低催化剂的还原温度,提高催化剂的比表面积,减小活性金属Ni的晶粒尺寸。随着Mn含量的增加,Ni-Mn/Al2O3催化剂的甲烷化性能先升后降,其中以Mn含量为4%(质量分数)时的催化甲烷化性能最佳,添加过量的Mn导致活性组分Ni被部分覆盖,催化甲烷化性能下降。通过对16Ni4Mn/Al2O3催化剂样品的浆态床反应温度及反应压力的研究发现,当反应温度为280℃、反应压力为1.5 MPa时,催化剂样品16Ni4Mn/Al2O3的CO转化率及CH4选择性分别达到96.2%和88.8%。  相似文献   

7.
采用浸渍和粉末压片的方法制备了两种ZrO2-Al2O3复合载体并用于负载Ni基催化剂,并利用氮气等温物理吸附、X射线粉末衍射(XRD)、H2程序升温还原(H2-TPR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等分析手段对催化剂物化性质进行表征,考察了ZrO2-Al2O3复合载体制备方法及ZrO2的引入对Ni基催化剂在CO、CO2和CO-CO2共存的3种体系下甲烷化反应活性的影响。材料表征和活性测试结果表明,在CO甲烷化体系中,与单一Al2O3载体相比,引入ZrO2的复合载体能有效提高催化剂中Ni物种的分散度从而增强CO甲烷化过程中催化剂活性,且粉末压片法较浸渍法制备的复合载体能有效提高催化剂的还原度,降低还原温度,但前者会大大降低催化剂的比表面积;在CO2甲烷化体系中,当载体形貌和制备方法相同时,载体的变化对催化剂活性的影响较小,CO2转化率主要受到制备方法不同引起的物理性质如比表面积变化的影响;在CO-CO2共存体系中,由于CO在竞争吸附中比CO2更容易占据活性位点,所以呈现出优先进行CO甲烷化再进行CO2甲烷化、CO2的含量先增多后减少的规律。  相似文献   

8.
田鑫  李欣  王薇  吕鹏  马保军 《现代化工》2022,(7):130-134+140
为了研究活性组分的负载对催化剂加氢脱硫性能的影响,设计并制备了Co/Si/Mo/Ni/Al2O3多元复合催化剂。通过固定床催化剂评价装置对其进行二苯并噻吩加氢脱硫反应活性评价,并利用X射线衍射仪(XRD)、N2吸附测试仪、X射线光电子能谱仪(XPS)、扫描电子显微镜(SEM)和Mapping等分析测试手段对催化剂进行表征。结果表明,复合催化剂具有优良的加氢脱硫性能,当活性组分负载量为(0.5%Co)/(1.5%Si)/(3.0%Mo)/(10.0%Ni)/Al2O3时,其加氢脱硫性能最高可达到96.1%。  相似文献   

9.
采用共沉淀法制备TiO2含量不同的TiO2-Al2O3复合载体,以传统的浸渍法制备活性金属负载量相同的NiMo/TiO2-Al2O3催化剂。运用N2低温吸附法、X射线衍射、H2程序升温还原和激光拉曼光谱等方法对催化剂进行表征,在10 mL微型反应装置上进行催化剂活性评价。结果表明,当复合载体中TiO2含量达到一定值后,TiO2在整个TiO2- Al2O3体系中的存在状态由高度分散转变为表面富集,XRD能够检测出锐钛矿型TiO2的特征峰;TiO2的添加对于催化剂的酸性能没有明显改变;激光拉曼光谱分析结果表明,TiO2的存在有利于生成八面体结构的钼物种,并在TiO2质量分数为8%时加氢脱硫活性达到较高水平。  相似文献   

10.
邓凡锋  黄星亮  于晨  侯亚博  曾菁 《化工进展》2015,34(8):3044-3048
以Al2O3作为载体,采用等体积浸渍法制备了多种不同的金属氧化物催化剂,考察其低温选择加氢脱硫醚活性。以1-戊烯和叔丁基甲基硫醚的环己烷模型化合物为反应原料,考察助剂的添加对NiMo/Al2O3催化剂性能的影响,并筛选出选择加氢脱硫活性最优的催化剂;接着以FCC全馏分汽油进行150h的长周期实验考察最优催化剂的性能;通过SEM、XRD、H2-TPR、C4H4S-TPD、硫碳分析对催化剂进行了表征。实验结果表明:经过适当组合的三组分催化剂的选择加氢脱硫醚的性能有所改变,其中以NiMoZn/Al2O3催化剂的选择加氢脱硫醚性能最好,并在长周期试验中表现出很好的活性和稳定性。表征结果证实Zn的加入起到了分相作用,促进NiO向表面迁移;降低活性组分与载体间的强相互作用,有利于组分的还原;适宜的Zn含量有利于催化剂表面的活性相均匀分布;Zn促进催化剂对硫化物的吸附。  相似文献   

11.
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   

12.
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   

13.
Sulfidation of trimetallic CoNiMo/Al2O3 catalysts was studied by thermogravimetry at 400 °C under flow and pressure conditions. Results were compared with those obtained on prepared and industrial CoMo/Al2O3 and NiMo/Al2O3 catalysts. The amount of sorbed H2S on the sulfided solids was measured at 300 °C in the H2S pressure range 0–3.5 MPa at constant H2 pressure (3.8 MPa). The adsorption isotherms were simulated using a model featuring dissociated adsorption of H2S 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   

14.
After the test run of several months two kinds of commercial catalysts (NiMo/Al2O3 and CoMo/Al2O3) were examined in hydrodesulfurization (HDS) of straight run (SRGO) and nitrogen-removed gas oils, at 340 °C under 50 kg/cm2 H2. Hydrogen renewal between stages was attempted to show additional inhibition effects of the by-products such as H2S and NH3. Spent NiMo/Al2O3 and CoMo/Al2O3 catalysts showed contrasting activities in HDS and susceptibility to nitrogen species, according to their catalytic natures, compared to those of their virgin ones. HDS over spent NiMo/Al2O3 was significantly improved by removal of nitrogen species, while that over spent CoMo/Al2O3 was much improved by H2 refreshment. The activity for refractory sulfur species such as 4,6-dimethyldibenzothiophene was reduced more severely than that for the reactive sulfur species such as benzothiophenes over spent catalysts. The effects of both two-stage hydrodesulfurization and nitrogen-removal were markedly reduced over the spent NiMo when compared with those over virgin NiMo one. The acidity of the catalysts was correlated with the inhibition susceptibility by nitrogen species as well as H2S and NH3. Spent catalysts apparently lost their activity due to the carbon deposition, which covered the active sites more preferentially. The spent NiMo catalyst carried more deposited carbon with larger C/H ratio and nitrogen content. Higher acidity was found to be present on the NiMo catalyst, but this was greatly decreased by the carbon deposition. Additionally, the reactivity of nitrogen species in HDS was briefly discussed in relation to the acidity of the catalyst and its deactivation by carbon deposition.  相似文献   

15.
杨军 《工业催化》2016,24(2):46-50
以氧化铝为载体,Ni和Mo为金属活性组分,添加不同含量乙二胺四乙酸,采用等体积浸渍法制备系列Ni Mo(x)/Al_2O_3(x为乙二胺四乙酸与Ni物质的量比)重质油加氢处理催化剂,考察乙二胺四乙酸加入量对催化剂加氢脱氮性能的影响,并采用N_2物理吸附-脱附、XRD和HRTEM等对催化剂进行表征。结果表明,乙二胺四乙酸的加入增强了金属组分与氧化铝载体间的相互作用,降低了MoS_2活性相的堆垛层数和片层长度,促进了活性相的分散。乙二胺四乙酸与Ni物质的量比为0.5时,MoS_2活性相堆垛层数和片层长度达到良好的结合,对应的催化剂Ni Mo(0.5)/Al_2O_3具有最优的加氢脱氮性能。  相似文献   

16.
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   

17.
Catalytic performance of Ni/CeO2/Al2O3 catalysts prepared by a co-impregnation and a sequential impregnation method in steam gasification of real biomass (cedar wood) was investigated. Especially, Ni/CeO2/Al2O3 catalysts prepared by the co-impregnation method exhibited higher performance than Ni/Al2O3 and Ni/CeO2/Al2O3 prepared by the sequential impregnation method, and the catalysts gave lower yields of coke and tar, and higher yields of gaseous products. The Ni/CeO2/Al2O3 catalysts were characterized by thermogravimetric analysis, temperature-programmed reduction with H2, transmission electron microscopy and extended X-ray absorption fine structure, and the results suggested that the interaction between Ni and CeO2 became stronger by the co-impregnation method than that by sequential method. Judging from both results of catalytic performance and catalyst characterization, it is found that the intimate interaction between Ni and CeO2 can play very important role on the steam gasification of biomass.  相似文献   

18.
The preparation of alumina-supported β-Mo2C, MoC1−x (x≈0.5), γ-Mo2N, Co–Mo2C, Ni2Mo3N, Co3Mo3N and Co3Mo3C catalysts is described and their hydrodesulfurization (HDS) catalytic properties are compared to conventional sulfide catalysts having similar metal loadings. Alumina-supported β-Mo2C and γ-Mo2N catalysts (Mo2C/Al2O3 and Mo2N/Al2O3, respectively) are significantly more active than sulfided MoO3/Al2O3 catalysts, and X-ray diffraction, pulsed chemisorption and flow reactor studies of the Mo2C/Al2O3 catalysts indicate that they exhibit strong resistance to deep sulfidation. A model is presented for the active surface of Mo2C/Al2O3 and Mo2N/Al2O3 catalysts in which a thin layer of sulfided Mo exposing a high density of sites forms at the surface of the alumina-supported β-Mo2C and γ-Mo2N particles under HDS conditions. Cobalt promoted catalysts, Co–Mo2C/Al2O3, have been found to be substantially more active than conventional sulfided Co–MoO3/Al2O3 catalysts, while requiring less Co to achieve optimal HDS activity than is observed for the sulfide catalysts. Alumina-supported bimetallic nitride and carbide catalysts (Ni2Mo3N/Al2O3, Co3Mo3N/Al2O3, Co3Mo3C/Al2O3), while significantly more active for thiophene HDS than unpromoted Mo nitride and carbide catalysts, are less active than conventional sulfided Ni–Mo and Co–Mo catalysts prepared from the same oxidic precursors.  相似文献   

19.
In this work, we explored the potential of mesoporous zeolite-supported Co–Mo catalyst for hydrodesulfurization of petroleum resids, atmospheric and vacuum resids at 350–450°C under 6.9 MPa of H2 pressure. A mesoporous molecular sieve of MCM-41 type was synthesized; which has SiO2/Al2O3 ratio of about 41. MCM-41 supported Co–Mo catalyst was prepared by co-impregnation of Co(NO3)2·6H2O and (NH4)6Mo7O24 followed by calcination and sulfidation. Commercial Al2O3 supported Co–Mo (criterion 344TL) and dispersed ammonium tetrathiomolybdate (ATTM) were also tested for comparison purposes. The results indicated that Co–Mo/MCM-41(H) is active for HDS, but is not as good as commercial Co–Mo/Al2O3 for desulfurization of petroleum resids. It appears that the pore size of the synthesized MCM-41 (28 Å) is not large enough to convert large-sized molecules such as asphaltene present in the petroleum resids. Removing asphaltene from the resid prior to HDS has been found to improve the catalytic activity of Co–Mo/MCM-41(H). The use of ATTM is not as effective as that of Co–Mo catalysts, but is better for conversions of >540°C fraction as compared to noncatalytic runs at 400–450°C.  相似文献   

20.
The effects of fluorine, phosphate and chelating agents on hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) are reviewed. All three additives enhance the activity of NiMo/Al2O3 catalysts in HDN but have only a slightly positive or even a negative effect on the HDS activity of CoMo/Al2O3 and NiMo/Al2O3 catalysts. The positive effect on HDN is due to the enhancement of the hydrogenation of aromatic rings. On the other hand, these three additives diminish the rates of C–N bond breaking and alkene hydrogenation reactions.

All three additives are hard basic ligands that may interact strongly with hard acids such as coordinatively unsaturated Al3+ cations on the alumina surface. A strong interaction with the alumina support has several effects. First, molybdate and tungstate anions are no longer strongly bonded to the support and are predominantly present as polyanions, which can be easily sulfided to MoS2 and WS2 crystallites. The weaker interaction with the smaller support surface also leads to larger MoS2 and WS2 crystallites with a lower dispersion. Second, the Ni2+ and Co2+ cations will also interact more weakly with the alumina, and this makes the formation of Ni and Co promoter atoms in the catalytically active Ni–Mo–S and Co–Mo–S phases more efficient. Third, the weaker interaction of Mo and W with the support leads to a higher stacking of the MoS2 and WS2 crystallites and, thus, to the more active type II Ni–Mo–S and Co–Mo–S phases. The increased stacking is beneficial for geometrically demanding reactions such as the hydrogenation of aromatics. For less demanding reactions, such as alkene hydrogenation, aliphatic C–N bond breaking and thiophene HDS, the loss in dispersion is important.  相似文献   


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