Synthesis of dispersed molybdenum disulfide nano-catalysts and their performance in the hydrogenation of simulated oil slurry
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摘要: 以二烷基二硫代氨基甲酸钼（Mo-DTC）和六羰基钼（Mo（CO）6）为前驱体、水热法合成了分散型纳米MoS2，采用X-ray射线衍射（XRD）、透射电子显微镜（TEM）、X射线光电子能谱分析（XPS）和程序升温脱附法（NH3-TPD）等方法对其进行了表征。利用三种烯烃（辛烯、苯乙烯、反式二苯乙烯）、苯并噻吩和蒽等构建模拟油浆体系，结合气相色谱-质谱（GC-MS）分析，对分散型纳米MoS2的模拟油浆加氢处理催化性能进行了研究。结果表明，不同预处理条件下制备出的催化活性样品均为2H-MoS2，但各样品的结晶度、颗粒尺寸、硫化程度及其酸性质等均有所不同，其中，总酸量差别较小；以Mo-DTC和Mo（CO）6为前驱体的优选硫化条件分别为380℃/30 min和370℃/30 min，所得到的催化剂对烯烃和噻吩的加氢活性较高。其中，Mo-DTC基纳米MoS2催化剂的烯烃加氢饱和转化率高达98.10%，加氢脱硫率为94.51%，而蒽的部分加氢饱和转化率则较低，为29.47%，且无八氢蒽（8HN）或全氢蒽的生成。Mo（CO）6基纳米MoS2催化剂的加氢效果则略差，烯烃加氢饱和转化率为94.01%，加氢脱硫率为89.01%，对蒽的加氢饱和转化率为24.20%，无8HN或全氢蒽的生成。总体而言，由Mo-DTC所制备的MoS2催化剂具有烯烃高效饱和、含硫化合物高效脱硫、芳烃浅度加氢饱和的效果，且油浆加氢处理反应的选择性及催化稳定性均更高。Abstract: A series of dispersed nano molybdenum disulfide (MoS2) catalysts were prepared with molybdenum dialkyl dithiocarbamate (Mo-DTC) and molybdenum hexacarbonyl (Mo(CO)6) as the precursors by hydrothermal methods and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (NH3-TPD). By using a simulated oil slurry containing three kinds of olefins (octane, styrene and trans-dibenzylethene), benzothiophene and anthracene, the catalytic performance of nano MoS2 in the hydrogenation was investigated, with the help of gas chromatography-mass spectrometry (GC-MS). The results indicate that all the prepared catalysts are in the form of 2H-MoS2; however, their crystallinity, particle size, vulcanization degree, and acid property are influenced by the pretreatment conditions; the preferred vulcanization conditions for the Mo-DTC-and Mo(CO)6-based MoS2 catalysts are 380 ℃/30 min and 370 ℃/30 min, respectively, to achieve a relatively high activity in the hydrogenation of olefins and benzothiophene. Over the Mo-DTC-based nano-MoS2 catalyst, the saturation conversion of olefins hydrogenation is 98.10% and the hydrodesulfurization rate is 94.51%, whereas the saturation conversion of anthracene hydrogenation is 29.47%, without forming octahydroanthracene (8HN) or perhydroanthracene. In contrast, the activity of Mo(CO)6-based nano-MoS2 catalyst is slightly lower, with the saturation conversion of olefins hydrogenation being 94.01% and the hydrodesulfurization rate being 89.01%; similarly, the saturation conversion for anthracene hydrogenation is 24.20%, without 8HN or perhydroanthracene in the product. As a whole, in comparison with the Mo(CO)6-based MoS2 catalyst, the nano MoS2 catalyst derived from Mo-DTC displays higher efficiency in both olefins saturation and sulfur-containing compounds desulfurization, and low degree hydrogenation of aromatic hydrocarbons; moreover, it also exhibits higher hydro-treating selectivity for the catalytic cracking slurry and higher stability during hydrogenation.
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Key words:
- nano-MoS2 /
- hydrodesulfurization /
- olefin saturation /
- anthracene /
- benzothiophene
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图 1 不同预处理条件下硫化反应产物的XRD谱图
a: 370 ℃/30 min; b: 370 ℃/60 min; c: 370 ℃/90 min; d: 380 ℃/30 min; e: 380 ℃/60 min; f: 380 ℃/90 min; g: 390 ℃/30 min; h: 390 ℃/60 min
Figure 1 XRD patterns of sulfurized MoS2 catalysts of Mo-DTC (a) and Mo(CO)6 (b) under different pretreatment conditions
图 2 不同预处理条件下制备的MoS2的结晶系数α
(a): Mo-DTC-based MoS2；(b): Mo(CO)6-based MoS2
Figure 2 Crystallinity factor (α) of MoS2 catalysts prepared under different pretreatment conditions
图 3 不同预处理条件下合成MoS2的HRTEM照片
(a)/(e): Mo-DTC/370 ℃/90 min; (b)/(f): Mo-DTC/380 ℃/30 min; (c)/(h): Mo(CO)6/370 ℃/30 min; (d)/(g): Mo(CO)6/380 ℃/90 min
Figure 3 HRTEM images of the MoS2 catalysts prepared under different pretreatment conditions
图 4 纳米MoS2的线条尺寸
(a): Mo-DTC/380 ℃/30 min; (b): Mo-DTC/370 ℃/90 min; (c): Mo(CO)6/370 ℃/30 min
Figure 4 Strip size of various nano-MoS2 catalysts
图 5 不同预处理条件下合成MoS2的XPS谱图
(a)/(b): Mo-DTC-based MoS2 synthesized at 380 ℃ for 30 min; (c)/(d): Mo-DTC-based MoS2 synthesized at 370 ℃ for 90 min; (e)/(f): Mo(CO)6-based MoS2 synthesized at 370 ℃ for 30 min; (g)/(h): Mo(CO)6-based MoS2 synthesized at 380 ℃ for 90 min
Figure 5 XPS spectra of MoS2 catalysts prepared under different pretreatment conditions
图 6 不同预处理条件下所制得MoS2的NH3-TPD谱图
a: Mo-DTC/380 ℃/30 min; b: Mo-DTC/370 ℃/90 min; c: Mo(CO)6/370 ℃/30 min; d: Mo(CO)6/380 ℃/90 min
Figure 6 NH3-TPD profiles of the MoS2 catalysts of Mo-DTC-based MoS2 (a) and Mo(CO)6-based MoS2 (b)prepared under different pretreatment conditions
图 7 模拟油浆加氢饱和产物的GC-MS谱图
1: n-octane; 2: ethylbenzene; 3: cumene; 4: n-propylbenzene; 5: 1, 2, 3, 4-tetrahydro-1-methyl-naphthalene; 6:1-methylnaphthalene; 7: 1, 2-diphenylethane; 8: 9, 10-dihydroanthracene; 9: 1, 2, 3, 4-tetrahydroanthracene; 10: anthracene
Figure 7 GC-MS spectra of the hydrogenation saturation products of simulated slurry over the Mo-DTC (380 ℃/3 h)
图 8 不同反应条件下Mo-DTC基MoS2对模拟油浆中的烯烃加氢饱和效果
(a): hydrogenation saturation conversion rate of various olefins; (b): selectivity of hydrogenated saturated product alkanes a: pretreatment with Mo-DTC-based MoS2 at 370 ℃ for 90 min; b: pretreatment with Mo-DTC-based MoS2 at 380 ℃ for 30 min; c: pretreatment without catalyst
Figure 8 Hydrogenation saturation of olefins in simulated slurry oil over the Mo-DTC-based MoS2 catalyst under different reaction conditions
图 9 不同反应条件下Mo(CO)6基MoS2对模拟油浆的烯烃加氢饱和效果
(a): hydrogenation saturation conversion rate of various olefins; (b): selectivity of hydrogenated saturated product alkanes a: pretreatment with Mo(CO)6-based MoS2 at 370 ℃ for 30 min; b: pretreatment with Mo(CO)6-based MoS2 at 380 ℃ for 30 min; c: pretreatment without catalyst
Figure 9 Hydrogenation saturation of olefins in simulated slurry oil over the Mo(CO)6-based MoS2 catalyst under different reaction conditions
图 10 不同预处理条件下模拟油浆中蒽加氢饱和效果
(a): pretreatment with Mo-DTC-based MoS2; (b): pretreatment with Mo(CO)6-based MoS2; (c): pretreatment without catalyst
Figure 10 Hydrogenation saturation of anthracene in simulated slurry oil under different pretreatment conditions
图 11 模拟油浆中模型芳香烃分子蒽的催化加氢反应历程
Figure 11 Catalytic hydrogenation pathway of anthracene as a model aromatic compound in the simulated slurry oil
图 12 模拟油浆中苯并噻吩加氢脱硫效果
a: Mo-DTC based MoS2; b: Mo(CO)6-based MoS2 ; c: no catalyst
Figure 12 Sulfur removal effect of benzothiophene in the simulated slurry oil
图 13 加氢处理反应后MoS2的XRD谱图(a)和加氢处理反应前后结晶系数α变化(b)
a: Mo-DTC based MoS2 pretreatment under 380 ℃ for 30 min; b: Mo(CO)6 based MoS2 pretreatment under 370 ℃ for 30 min A: Mo(CO)6-based MoS2; B: Mo-DTC-based MoS2
Figure 13 XRD patterns of the MoS2 catalysts after hydro-treating reaction (a) and change in crystallinity factor (α) before and after hydro-treating reaction (b)
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