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 共查询到19条相似文献,搜索用时 140 毫秒
1.
采用FT-IR和程序升温热谱技术研究了Mo/HZSM-5催化剂的制备过程.结果表明Mo/HZSM-5样品在合适的温度下焙烧一定时间,Mo物种与HZSM-5分子筛的酸中心(主要是强酸中心)起作用,并且一部分Mo物种会迁移到分子筛孔道内.在外表面的Mo物种和在孔道内强酸中心作用的Mo物种,可能是对甲烷活化起作用的  相似文献   

2.
采用FT-RI和程序温热谱技术研究了Mo/HZSM-5催化剂的制备过程。结果表明Mo/HZSM-5样品在合适的温度下焙烧一定时间,Mo物种与HZSM-5分子筛的酸中心起作用,并且一部分Mo物种会迁移到分子筛道内。  相似文献   

3.
27Al和29Si MAS-NMR对Mo/HZSM-5催化剂的研究   总被引:3,自引:0,他引:3  
使用^29Al固体离分辨核磁技术对甲烷无氧芳构化催化剂Mo/HZSM-5分子筛进行了研究,发现HZSM-5分子筛本体中仅含有少量非骨架Al,Mo物种与分子筛骨架Al的相互作用随Mo担载量以及焙烧的温度的升高而增加,在高温焙烧下,Mo物种会使分子筛骨架严重脱铝,并且生成Al2(MoO4)3新相,最终导致分子筛骨架塌陷,催化性能下降。  相似文献   

4.
Fe—Mo/KZSM—5上甲醇氧化为甲醛的研究   总被引:1,自引:0,他引:1  
李景林  李斌 《催化学报》1999,20(4):429-432
采用浸渍法制备了Fe/Mo/HZSM-5和Fe-Mo/KZSM-5分子筛催化剂,利用NH3-TPD和O2-TPD对催化剂的表面酸性和吸附O2物种进行了表征,考察了温度、Mo/Fe摩尔比,空气/甲醇摩尔比及WHSV对催化性能的影响。实验结果表明,在Fe-Mo/KZSM-5催化剂上,适宜的反应条件下,甲醇转化率接近100%,甲醛选择性达到90.6%,同时还进行了96h的催化剂的稳定性实验。  相似文献   

5.
甲烷无氧芳构化制芳烃双功能催化剂的研究   总被引:2,自引:0,他引:2  
以 Mo/HZSM-5作为甲烷无氧芳构化的金属一酸双功能催化剂,研究了 HZSM-5 分子筛表面的硅酯修饰对Mo物种的分散状态、配位结构及催化剂的催化性能的影响, 并通过水汽处理调变分子筛的酸性,考察了催化剂的积炭行为同酸强度分布的关系. 并发现分子筛表面的中性端式硅羟基或酸性桥式铝羟基与Mo物种结合对Mo物种的分 散状态和配位结构有不同影响.XPS和H_2-TPD结果表明,浸渍Mo组分之前对分子筛 表面进行硅酯修饰以覆盖其外表面的部分铝羟基可以显著提高Mo物种的分散度,说明 硅羟基对Mo物种的分散有利,而与铝羟基结合则不利于Mo物种的分散.ESR结果表 明,催化剂表面大部分Mo物种与分子筛的铝物种之间无直接相互作用,这部分Mo物 种以六配位为主,容易被还原为碳化钼活性相;与分子筛的铝物种之间存在强相互作 用的那部分 Mo物种则以四配位和五配位为主,不易被还原为碳化钼活性相,对反应不 利,硅酯修饰使六配位的Mo物种增多,减少了四配位Mo物种的生成,使催化剂的活 性有所提高,但对积炭行为影响很小.反应过程中积炭主要在分子筛的酸中心上生成. NH3-TPD与 TPO结果表明,在MO/HZSM-5的酸中心上主要生成两类不同H/C比  相似文献   

6.
甲烷在MoO3/HZSM-5分子筛催化剂上的非氧催化转化   总被引:17,自引:3,他引:14  
研究了反应温度、空速、Mo担载量和焙温度对MoO3/HZSM-5催化剂上甲烷的芳构化反应的影响。HZSM-5分子筛的Bronsted酸性、孔道结构和Mo在分子筛中的分布是影响催化性能的重要因素,HZSM-5上Mo担载量为2-3%时活性最佳,在1013K反应温度下甲烷转化率可达9%,芳烃选择性大于90%,空速影响的实验表明乙烯明反应的初始产物,在此基础上提出了“甲烷酸助异裂活化”的新概念、“金属相类  相似文献   

7.
刘自力  林维明 《分子催化》1999,13(3):226-228
高温下,甲烷在Mo/HZSM-5分子筛上可直接生成苯[1].虽然低温下甲烷能被Mo/HZSM-5催化剂表面的—OH所活化[2],但对甲烷在高温下的活化过程知之甚少,然而这却是很重要的.我们采用原位红外光谱技术,研究了甲烷在高温下Mo/HZSM-5催化...  相似文献   

8.
预处理条件对Mo/HZSM—5催化剂上丙烷芳构化的影响   总被引:1,自引:0,他引:1  
采用浸渍法制备了Mo/HZSM-5 分子筛催化剂,考察了H2 、N2 、空气预处理对催化剂丙烷芳构化活性的影响。在相同处理条件下,空气气氛更有利于提高催化剂的丙烷芳构化活性。在空气焙烧过程中,氧化钼物种向分子筛内表面分散。在H2 还原处理过程中,表面钼物种部分被还原为Mo4 + 。随还原时间延长,催化剂芳构化活性升高,同时发生少量Mo 物种向分子筛孔道内迁移  相似文献   

9.
研究了反应温度、空速、Mo担载量和焙烧温度对MoO3/HZSM-5催化剂上甲烷的芳构化反应的影响.HZSM-5分子筛的Bronsted酸性、孔道结构和Mo在分子筛中的分布是影响催化性能的重要因素.HZSM-5上Mo担载量为2~3%时活性最佳,在1013K反应温度下甲烷转化率可达9%,芳烃选择性大于90%.空速影响的实验表明乙烯是反应的初始产物.在此基础上提出了"甲烷酸助异裂活化"的新概念、"金属钼类碳烯中间物"的新观点和甲烷芳构化的可能机理.  相似文献   

10.
甲烷无氧脱氢芳构化催化剂Mo/HZSM-5的研究   总被引:9,自引:1,他引:9  
催化剂Mo/HZSM-5在甲烷地氧脱氢芳构化反应中表现出很高的活性,用XRD,BET经表面,NH3-TPD及TPR等手段,对不抽提前后催化剂上的活性o的种进行了研究,XRD结果表明,Mo物种高度分散于筛表面,随着Mo担载量的提高,BET比表面积有所下降;但氨水抽提后,比表面积有很大程度的恢复,NH3-TPD结果表明,Mo物种优先占据分子筛中的强酸位。TPR结果显示出有MoO3晶相存在的催化剂较易被  相似文献   

11.
Impregnation, mechanical mixing and hydrothermal treatment methods were used to introduce molybdenum species into the HZSM-5 zeolite. The structure and surface acidity of the catalysts were studied by means of XRD, FT-IR, NH3-TPD, TPR and XPS. The effects of Mo content and reaction time on stream on the aromatization of propane were investigated. It was found that the performance of the Mo/HZSM-5 catalyst prepared by the hydrothermal treatment method was much better than that of the other two catalysts. For example, under the reaction conditions of 823 K and 600 h-1, propane conversion and aromatics selectivity over the catalyst prepared by hydrothermal pretreatment could reach 89.17% and 78.56%, respectively. XRD and XPS results showed that the Mo species in the catalysts prepared by hydrothermal treatment were highly dispersed on the surface of the HZSM-5, and larger amounts of them could penetrate into the HZSM-5 channel, as compared with the other two kinds of catalysts. These factors may be responsi  相似文献   

12.
Impregnation,mechanical mixing and hydrothermal treatment methods were used to introduce molybdenum species into the HZSM-5 zeolite ,the structure and surface acidity of the catalysts were studied by means of XRD,FT-IR ,NH3-TPD,TPR and XPS,The effects of Mo content and reaction time on stream on the aromatization of propane were investigated,It was found that the performance of the Mo/HZSM-5 catalst prepared by the hydrothermal treatment method was much better than that of the other two catalysts,For example ,under the reaction conditions of 823 K and 600h^-1, propance conversion and aromatics selectivity over the catalyst prepared by hydrothermal pretreatment could reach 89.17% and 78.56%,respectively,XRD and XPS results showed that the Mo species in the catalysts prepared by hydrothermal treatment were highly dispersed on the surface of the HZSM-5,and lartger amounts of them could penetrate into the HZSM-5 channel ,as compared with the other two kinds of catalysts,These factors may be responsibled for their high activities for propane aromatization,IR and NH3-TPD studies indicated that the number of Broensted acid centers decreased and the Lewis acid centers increased after Mo was introduced into the HZSM-5 zeolite.  相似文献   

13.
La/HZSM—5催化剂上丙烷的芳构化反应研究   总被引:5,自引:0,他引:5  
采用浸渍法和离子交换法制备了La/HZSM-5分子筛催化剂,用于丙烷芳构化反应,利用XRD,SPS,FT-IR,NH3-TPD技术考察了La对HZSM-5分子筛结构和表面酸性的影响,引入La后能显著提高HZSM-5的丙烷芳构化活性,其中由离子交换法得到的催化剂效果最佳,在反应温度550度,空速600h^-1条件下,丙烷转化率和芳烃选择性分别达到94.58%,68.99%,在La/HZSM-5中分子筛结晶度下降,B酸中心减少,L酸中心增多,离子交换法制备的催化剂比浸渍法催化剂的这种变化更显著,同时更有利于La3 进入分子筛孔道内,并与分子筛产生强相互作用,新增加的L酸中心可能是芳构化反应的活性中心。  相似文献   

14.
The influence of adding Fe,Cr,Co,and Ga into 3%Mo/HZSM-5 catalyst on methane aromatization,and the influence of additives ratio on methane conversion,selectivity to hydrocarbons and coke,as well as distribution of aromatics were investigated.The experimental results showed that the addition of Fe,Cr,Co and Ga promoted the dehydrogenation and dissociation of methane.The results of NH3-TPD indicated that the acidity of HZSM-5 was changed by adding Fe and Co components,consequently the catalytic properties of Mo/HZSM-5 were changed.It was also revealed that strong acid sites were the center of methane aromatization.The results of XRD characterization showed that the crystallinity of Mo on ZSM-5 zeolite was increased after adding Fe,Co additives.  相似文献   

15.
碳四烃在改性HZSM-5分子筛上芳构化研究   总被引:8,自引:0,他引:8  
研究了炼厂混合C_4烃在Zn、Ga、Cr、La改性的HZSM-5分子筛催化剂上的芳构化反应,采用TPD和IR测定了催化剂的表面酸性质。结果表明,用Zn(3%)和Zn(2%)Ga(1%)改性的HZSM-5分子筛具有较好的芳构化性能;各改性HZSM-5分子筛催化剂芳构化性能变化与表面酸性有关,总酸量下降,芳构化活性下降,强B酸中心减少,深度裂解反应减少;Zn的单组分和双组分改性的HZSM-5分子筛催化剂芳构化活性的增高与表面强L酸浓度增加和吡啶吸附IR谱中的1615cm~(-1)吸收峰出现有关。  相似文献   

16.
A Mo-promoted Zn/HZSM-5 catalyst was prepared by isometric impregnation method (IM). The physicochemical properties of catalysts were characterized by X-ray diffraction, registration of N2 adsorption-desorption isotherms, transmission electron microscopy, NH3 temperature-programmed desorption and IR spectroscopic study of pyridine adsorption. The results show that by doping zeolite with Mo species it is possible to tune the microstructures, acidity and crystallinity of the catalyst. Additionally, it was found that the 1%Mo(IM)–5%Zn(IE)/HZSM-5 catalyst had a high catalytic activity and stability for methanol to aromatics (MTA) reaction. The yield of aromatics reached 77.3% at 450°C and TOS = 3 h. When the TOS = 98 h, the yield of total aromatics remains at a 60.4% level. The lifetime of catalysts was influenced by the synergetic effect of Brønsted and Lewis acid sites, so the modification with Mo may bring an opportunity to prolong the lifetime of Zn/HZSM-5 catalyst in the MTA reaction. The metal components are sintered and lost in continuous reaction-regeneration cycles. Accordingly, the activity of deactivated catalyst cannot be completely restored to the initial level.  相似文献   

17.
18.
The promotional effect of Fe-Mo species introduced into HZSM-5 (Zeolyst Int., SiO2/Al2O3 ≈ 30) zeolite catalyst by the wetness impregnation method for the 1-hexene aromatization was investigated. The structure and catalytic performance for the aromatization of 1-hexene over xFeyMo-ZSM-5 catalysts in comparison with unmodified HZSM-5 catalysts were studied. The xFeyMo-ZSM-5 catalysts contain fixed loading (5 wt%) and variable Fe/Mo ratio. The catalysts were characterized by BET, ICP-AES, HRSEM-EDS, HRTEM, XRD, FTIR, H2-TPR, NH3-TPD, and pyridine DRIFT spectroscopy. The characterization data confirmed the existence of Fe and Mo species in the zeolite matrix. With Fe and Mo species implementation to HZSM-5 zeolite, the amount of the acid sites decreased, but the selectivities to C9+ aromatics increased. The catalyst evaluation was performed at 350 °C for 6 h on-stream at atmospheric pressure using a fixed-bed quartz tube reactor. The selectivity to products of different carbon number was affected by the Fe/Mo ratio within the zeolite. It was found the product distribution of grouped fractions of C1–C17+ from the liquid product. The results indicate that the optimum ratio of Fe/Mo is 1–1.5. The highest selectivity for gasoline and distillate ranges was obtained for the 2.5wt%Fe2.5wt%Mo- and 3wt%Fe2wt%Mo-ZSM-5 samples, which was higher than that for parent HZSM-5 catalyst.  相似文献   

19.
改性纳米ZSM-5催化剂上正辛烷转化反应的研究   总被引:4,自引:0,他引:4  
以纳米晶粒HZSM-5(20~50 nm)沸石为活性组分, 用碱性介质水热处理、 负载混合稀土和ZnO(或GaO)组合改性方法对纳米HZSM 5分子筛进行改性, 并用TEM, XRF, IR及XRD等手段对催化剂进行表征. 以正辛烷的芳构化和异构化为模型反应, 研究了改性纳米ZSM 5催化剂总酸和酸强度分布、 L/B酸位比例对正辛烷异构化和芳构化反应性能的影响以及催化剂酸强度、 L/B酸位比例与催化剂稳定性和积炭的关系. 结果表明, 碱性介质水热处理和混合稀土改性后, 总酸量减少和酸强度降低导致纳米HZSM-5催化剂的芳构化活性减弱, 异构化活性增强, 稳定性明显提高. 在碱性介质水热处理和负载混合稀土改性的基础上, 再负载适量氧化锌(或氧化镓)改性的催化剂, 总酸量增加, 强酸中心数量减少, B酸略有减少, 而L酸明显增加, L/B酸位比值增加. L酸中心和B酸中心的协同作用和较合适的L/B(1.4~1.7)比值使改性的纳米ZSM-5催化剂保持了较强的和稳定的芳构化和异构化活性, 催化剂积炭失活速率降低. 芳烃和异构烷烃产率分别达到约50%和30%, 高辛烷值的烷基芳烃(C7~C9)和异构烷烃(C4~C6)的选择性分别达到84%和80%.  相似文献   

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