共查询到17条相似文献,搜索用时 93 毫秒
1.
通过调变六次甲基四胺与金属钼盐的摩尔比例,以络合物分解法制备了碳氮夹杂钼基催化剂,并将其负载于氧化铝载体上.采用X射线衍射(XRD)、X射线光电子能谱(XPS)、低温氮吸附、元素分析等方法对催化剂进行了表征,发现碳氮夹杂钼基催化剂实为碳化钼(β-Mo2C)与碳氮化钼(M02CxNy)的混合物.以二苯并噻吩(DBT)的加氢脱硫反应(HDS)为探针,比较了负载型碳化钼、氮化钼及碳氮夹钼基催化剂的催化活性,发现由于夹杂催化剂中含有新的活性相Mo2CxNy。而表现出高于碳化钼和氮化钼催化剂的催化活性. 相似文献
2.
一种新型的磷化钼加氢精制催化剂的研究 总被引:8,自引:0,他引:8
通过(NH4)Mo7O24·4H2O和(NH4)2HPO4水溶液沉淀、焙烧在923K用H2还原制得磷化钼催化剂.XRD检测表明,用H2还原后有纯的磷化钼生成.在3.0MPa的高压连续微反系统中测定催化剂的加氢活性.以制备的磷化钼为活性组分、γ-Al2O3为稀释剂,考察了空速、反应温度和反应时间对模型化合物的HDN、HDS和HDY性能的影响,结果表明:在合适的条件下,其脱硫脱氮率可达到90%以上.模型化合物为吡啶、噻吩和环己烯,吡啶含量以N计(为0.2%)、噻吩含量以S计(为0.3%),环己烯含量为20%,以环己烷作溶剂. 相似文献
3.
碳化钼催化剂加氢脱氮性能研究 总被引:3,自引:3,他引:0
MoO3在CH4/H2气氛中程序升温还原碳化反应制备了Mo2C催化剂,用XRD、BET、SEM、XPS进行了表征。以吡啶/环己烷溶液为模型化合物,在高压微反装置上评价了碳化钼催化剂的吡啶加氢脱氮性能。结果表明,MoO3在CH4/H2气氛中程序升温至675℃可制得高纯度的β-Mo2C,SEM表征其形貌为板块状颗粒,平均粒径约3.9μm,比表面积达到了10.7m2/g,高于其前驱体MoO3 的2.7倍。在反应压力3.0MPa,空速为8h-1,H2/原料液体积比为500∶1,体积分数为5%的吡啶/环己烷溶液中,碳化钼催化剂在340℃下的吡啶加氢脱氮转化率达到了86.30%,高于相应MoS2约8%。随还原碳化温度的升高,碳化钼催化剂的比表面积降低,表面积炭增多,导致其吡啶加氢脱氮活性下降。确定的碳化钼催化剂的合成条件以还原碳化温度675℃、还原碳化气体空速1.8×104h-1左右较为适宜。 相似文献
4.
制备条件对磷化钼加氢脱硫催化活性的影响 总被引:1,自引:1,他引:0
采用程序升温还原方法制得磷化钼(MoP)催化剂,在常压连续微型化反应装置中,以噻吩为模型化合物,对催化剂的加氢脱硫活性进行评价。考察了还原温度、磷钼摩尔比、不同磷源等制备条件对MoP催化活性的影响。实验结果表明,在MoP生成温度区间内,随着还原温度的升高,催化剂活性降低;磷钼摩尔比为1∶1时,噻吩转化率最高,而磷钼摩尔比为1∶2和2∶1时制备催化剂的催化活性相当;采用磷酸二氢铵、磷酸铵以及磷酸为磷源,均可制得磷化钼,而以磷酸二氢铵为磷源时制备磷化钼催化剂的活性最佳。在噻吩加氢脱硫反应条件下反应后,不同磷源制备的磷化钼整体物相均没有发生变化。 相似文献
5.
6.
用浸渍法制备出γ- Al2 O3 负载不同 Co/( Co+ Mo)比的 Co Mo氧化物 ,以其作为前驱体 ,在 N2 - H2混合气体中程序升温反应 ,合成出一系列 Co Mo Nx/γ- Al2 O3 催化剂 .用二苯并噻吩 ( DBT)的加氢脱硫作为模型反应 ,评价了催化剂的催化活性和选择性 .研究表明 ,Co Mo Nx/γ- Al2 O3 催化剂催化 DBT的脱硫有两条途径 :一是直接氢解脱硫 ,产物为联苯 ;另一途径是 DBT上的苯环先加氢然后脱硫 ,主要产物是环己基苯 .其中 ,第一条途径为主要反应 .不同的预处理条件对催化剂的活性和选择性有明显影响 ,预还原并未提高催化剂的活性 ,预硫化却减低了产物的选择性 .在较宽的 Co/( Co+ Mo)比范围内 ,Co Mo Nx/γ- Al2 O3催化剂都显示出较高的催化活性 相似文献
7.
8.
9.
非负载型磷化钼加氢精制催化剂的研制 总被引:9,自引:0,他引:9
尽管有相当多的文献和专利报道了含磷加氢精制催化剂的研究及磷的加入对Mn-Ni、Ni-Mo、Ni-W、Co-Mo、Mo、W、Ni、Co等各类加氢精制催化剂结构、及HDS、HDN活性的影响,并证明了磷或含磷化合物可作为加氢精制催化剂的助剂和稳定剂,但对于磷化物加氢催化剂的合成及对其HDS、HDN活性的研究还很少。本文在较低温度下用氢气直接还原磷钼酸铵盐得到非负载型的磷化钼催化剂,并以制备的磷化钼为活性组分,以SiC和γ-Al2O3为稀释剂,选择高浓度和低浓度的吡啶、噻吩和环己烯的混合物为模型化合物,以环己烷作溶剂,测定了制备催化剂的HDS、HDN及HYD活性。结果表明,所研制的非负载型磷化钼加氢精制催化剂对两种含有吡啶、噻吩和环己烯的模型化合物具有同时HDN, HDS 和 HYD的性能。 相似文献
10.
钴掺杂对碳化钼催化噻吩加氢脱硫性能的影响 总被引:2,自引:0,他引:2
以MoO3和CoMo混合氧化物为前驱体, 制备了碳化钼和碳化钼-钴催化剂, 采用XRD, BET, SEM和XPS等技术对其进行了表征, 研究了Co掺杂对碳化钼催化剂噻吩加氢脱硫性能的影响. 结果表明, 掺入适量的Co后制得的CoMo双金属混合氧化物为MoO3和CoMoO4的两相混合体, 经CH4/H2气氛程序升温还原碳化反应生成共生共存的Co-Mo2C, Co以金属细颗粒的形态均匀地分散在生成的Mo2C组分之间. 在共生过程中含Co物种的掺入可降低制备碳化钼所需要的还原碳化温度, 使制备的碳化钼颗粒变小, 比表面积增大, 表面Mo2+含量增多, 从而对碳化钼的噻吩加氢脱硫活性有较好的促进作用, Co的添加量以Co/Mo摩尔比为0.2左右较为适宜. 用化学共沉淀法制得的Co-Mo2C共生共存体系的噻吩加氢脱硫反应活性, 好于由金属Co与Mo2C机械混合法制得的Co+Mo2C二相共存体系. 这表明当两个活性相共存时, 只有经过相互共生过程才能发挥其最佳的协同效应. 相似文献
11.
Cummins CC 《Angewandte Chemie (International ed. in English)》2006,45(6):862-870
Anionic terminal one-atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low-coordinate phosphorus centers in the protecting coordination sphere of the metal complex. Salt-elimination reactions with chlorophosphanes lead to phosphaisocyanide, iminophosphinimide, and diorganophosphanylphosphinidene complexes in which the unusual phosphorus ligands are stabilized by coordination. X-ray structure analyses and density-functional calculations illuminate the bonding in these compounds. 相似文献
12.
Kinetics and mechanism of oxidation of silicon nitride bonded silicon carbide ceramic 总被引:1,自引:0,他引:1
Thermogravimetry (TG) has been used to study the oxidation of a commercial silicon nitride bonded silicon carbide (SNBSC) ceramic. The oxidation was studied in air and carbon dioxide atmospheres between 800 and 1300°C. TG/mass spectrometry (MS) shows that the silicon nitride bonding phase oxidises first. The kinetics follow a multi-stage mechanism with diffusion control. Carbon dioxide was found to be a more powerful oxidant than air at temperatures above 1050°C. 相似文献
13.
Man Zheng Bohan Cao Jiaxian Liu Kun Shi Yufan Zhang Huan Wang 《Electroanalysis》2023,35(7):e202200519
In this study, a simple method was designed to prepare ordered mesoporous carbons embedded with molybdenum without any extreme conditions. We prepared three different ordered molybdenum carbide materials with mesoporous structures to explore the influence of the structure of molybdenum-based materials on the HER catalytic efficiency. The ordered mesoporous molybdenum carbide catalysts (CMK-3-MoCx, fCMK-3-MoCx, CMK-8-MoCx) were characterized by SEM, TEM, XRD, nitrogen adsorption-desorption and XPS. The HER is catalyzed efficiently on the three electrocatalysts, fCMK-3-MoCx shows the best HER electro-catalytic performance with a small onset potential of −0.06 V vs. RHE, a low tafel slope of 66 mV dec−1 and a small over-potential value of 89 mV at 10 mA cm−2. This excellent performance on HER is due to its high specific surface area and highly ordered mesoporous structure that resulted in excellent proton transport efficiency and high electron transfer rate. Our results provide a new research direction for the application of flat ordered mesoporous structures in catalysis. 相似文献
14.
负载型磷化镍催化剂的溶剂热法制备及其加氢脱硫性能 《燃料化学学报》2015,43(6):714-719
以廉价的三苯基膦(PPh3)为磷源,以三正辛胺(TOA)为液相反应体系,溶剂热法制备了负载型Ni2P/MCM-41催化剂,并采用XRD、BET、CO吸附、XPS和TEM等手段对制备得到的催化剂进行了表征。该方法的合成温度为330 ℃,反应在常压下进行,比程序升温还原法(H2-TPR)所需的还原温度至少低300 ℃,比传统的溶剂热法合成原料更廉价。以二苯并噻吩(DBT)为模型化合物,比较了所制备的Ni2P/MCM-41催化剂与H2-TPR法制备的催化剂结构以及加氢脱硫(HDS)性能。结果表明,溶剂热法能够降低催化剂表面上P物种的集聚,从而得到较大比表面积的Ni2P催化剂(690 m2/g);促进小尺寸、高度分散的Ni2P活性相的生成;制得的催化剂的HDS活性明显高于H2-TPR法催化剂,在反应温度340 ℃,质量空速2.0 h-1,H2/油=500(体积比),3.0 MPa的条件下,Ni2P/M41-R催化剂DBT转化率达到96.8%,较H2-TPR法高10.6%。 相似文献
15.
《Arabian Journal of Chemistry》2020,13(5):5199-5207
Here in, for the first time we are reporting molybdenum carbide reduction into metallic molybdenum during methane aromatization on HZSM-5 (Si/Al ratio = 23, 30, 50 and 80) at methane space velocity of 1800 mL.gcat−.h−. Benzene yield was influenced by the surface metallic molybdenum through the non-aromatic carbon deposits formation via linear hydrocarbons degradation on HZSM-5 with fewer acidity (Si/Al ratio = 30, 50 and 80). Our XPS analysis results demonstrated improved surface metallic molybdenum in spent Mo2C/HZSM-5 = 80 (0.71 atom. %) and 50 (0.54 atom. %) samples over Mo2C/HZSM-5 = 30 (0.33 atom. %) and 23 (0.20 atom. %) samples. Furthermore, HR-TEM and FFT analysis images clearly established fine distribution of distorted spherical shaped Mo2C particles with 6–14 nm size in spent Mo2C/HZSM-5 = 23. On the other hand, Mo2C particle size was increased upto 22 nm in Mo2C/HZSM-5 = 80. The ease reduction of Mo2C into metallic molybdenum and aggregation of Mo2C particles in spent higher Si to Al ratio (50 and 80) samples was associated with weak interactions between Mo2C and the HZSM-5 with fewer acidity. At 700 °C, the order of benzene yield as follows: Mo2C/HZSM-5 = 80 (2.2%) < Mo2C/HZSM-5 = 50 (3.25%) < Mo2C/HZSM-5 = 30 (5.2%) < Mo2C/HZSM-5 = 23 (8.0%). 相似文献
16.
XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The X-ray photoelectron spectroscopy (XPS) was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo_2C and α-MoC_(1-x) pretreated by syngas at different temperatures, and the promotional effect of potassium on the catalytic performance was also studied. XPS results revealed that the content of surface Mo and its valence distribution between β-Mo_2C and α-MoC_(1-x) were quite different. Promoted by potassium, the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo_2C. Potassium had strong electronic effect on β-Mo_2C, which led to a higher Mo~(4+) content. On the contrary, potassium had little electronic effect on α-MoC_(1-x), and K-Mo interaction was weak. Therefore, Mo~0 and Mo~(2+) became the dominant species on the catalyst surface, and the Mo~(4+) content showed almost no increase as the pretreatment temperature enhanced. In terms of catalytic performance of molybdenum carbides, the increase in Mo~0 most likely explained the increase in hydrocarbon selectivity, yet Mo~(4+) might be responsible for the alcohols synthesis. 相似文献