甲烷芳构化反应催化剂Ｍｏ-Ｍ／ＨＺＳＭ-５表面性质的研究

对甲烷芳构化催化剂Ｍｏ-Ｍ／ＨＺＳＭ-５进行了异丙醇分解、ＮＨ３-ＴＰＤ-ＭＳ、积炭量测定表征,其结果均与芳构化性能有关。芳烃收率高,稳定性好,积炭量较少,而且具有相当量的酸量和一定量强酸量及较强的脱氢中心。     

Methane aromatization over Mo/H-ZSM-5: on the reaction pathway

Rates of benzene formation on Mo/HZSM-5, H-ZSM-5 and Mo/SiO₂ were measured with different reactants: methane, mixture of C₂H₄/H₂/N₂ and mixture of C₂H₂/H₂/N₂. Since the rate of benzene formation starting from C₂H₄/H₂/N₂ is higher on Mo/H-ZSM-5 compared to H-ZSM-5 it is concluded that the aromatization of methane on Mo/H-ZSM-5 is not going via ethylene which is aromatized over acid sites. Another reaction pathway is proposed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Methane Aromatization over 2 wt% Mo/HZSM-5 in the Presence of O2 and NO

In the non-oxidative aromatization reaction (temperature = 770 C, flow rate = 34 ml min^-1), 2 wt% Mo/HZSM-5 deactivated after 4 h due to severe coking. We observed that with a suitable amount of O₂ (5.3 vol%) in the methane feed, the catalyst could last for more than 6 h with a ca. 4% yield of aromatics at 770 °C. Depending on the concentration of O₂ or the reaction temperature, there are three reaction zones in the catalyst bed: (i) methane oxidation; (ii) methane reforming; and (iii) methane aromatization. CO and H₂ produced in the first two zones are accountable for stability amelioration of the catalyst. The addition of NO exhibited similar effects on the reaction. Further increase in O₂ (8.4 vol%) or NO (14.2 vol%) concentration would result in CO and CO₂ being the predominant carbon-containing products; C₂H₄ and C₂H₆ were generated in small amounts and no aromatics were detected.     

Mo/HZSM-5上甲烷无氧芳构化催化剂制备因素的考察

采用Mo/HZSM-5作为甲烷无氧芳构化催化剂,考察了催化剂制备部分影响因素.结果表明,采用较低的nSi:nAl时(25)载体制备的催化剂活性和稳定性较好;浸渍法优于固相反应法;Mo担载的质量分数为4%时,催化剂表现出最高活性;分子筛预先经碱处理,能够明显改善催化剂稳定性.     

FCC汽油在纳米HZSM-5上芳构化降烯烃反应研究

介绍了纳米HZSM-5沸石分子筛催化剂用于FCC汽油馏分(75～120) ℃降烯烃芳构化的研究结果以及操作条件对反应性能的影响。结果表明,最佳的操作条件为反应温度430 ℃,压力0.3 MPa,液时空速1.0 h^－1。对该催化剂的失活再生性能进行了研究,结果表明,失活催化剂经过一次和两次再生后,其降烯烃芳构化性能基本保持不变。     

Methane dehydrogenation and aromatization over 4 wt% Mn/HZSM-5 in the absence of an oxidant

Methane dehydrogenation and aromatization over 4 wt% Mn/HZSM-5 in the absence of an oxidant (GHSV = 1600 mL h⁻¹ g⁻¹) was investigated. Mn/HZSM-5 was prepared by impregnation of HZSM-5 with manganese acetate tetrahydrate solution; Mn₃O₄ formed was the precursor of active phase for methane activation. The induction period over Mn/HZSM-5 catalyst before aromatic products appear was long at 700 °C. This period shortened with a rise of the reaction temperature to 800 °C. XPS and TPO results showed that the partly carburized or carburized Mn species formed are probably responsible for methane activation.     

钇对甲烷芳构化催化剂Mo／HZSM—5性能影响的研究

研究了稀土钇的含量对Ｍｏ／ＨＺＳＭ－５催化剂的活性和选择性的影响，发现稀土钇的加入，不同程度上提高了Ｍｏ／ＨＺＳＭ－５的活性和选择性。特别是，当Ｙ／Ｍｏ＝０．０４时，活性最佳。甲烷在１０２３Ｋ芳构化反应，转化率达１９．６％，苯的选择性达９６．５％，且活性较稳定。     

改性Mo/HZSM-5催化剂甲烷无氧芳构化反应条件研究

采用Mo担载的质量分数为6%、经过先碱后酸预处理的Mo/HZSM-5作为催化剂,在不同反应温度和反应空速下,比较了甲烷的转化率、苯的生成速率和积炭的收率.结果表明,当反应温度为700℃,反应空速为1 400 mL/(g·h)时,甲烷无氧芳构化性能最佳.     

Methane dehydroaromatization over Mo/HZSM-5: A study of catalytic process

The deactivation process of methane dehydroaromatization (MDA) reaction has been followed by various physical chemistry methods.     

Zn 助剂对WC/HZSM-5催化正己烷芳构化性能影响

以WC/HZSM-5为前驱体制备了一系列不同Zn含量的Zn-WC/HZSM-5催化剂,采用X射线衍射、扫描电子显微镜、N₂物理吸附、傅里叶变换红外光谱和热重分析等手段对Zn-WC/HZSM-5的晶相、形貌、比表面积、酸性质、积炭量等进行了表征,并研究了正己烷芳构化的催化性能,探究了助剂Zn与WC在反应过程中的作用。结果表明,Zn的引入可以提高催化剂的芳烃选择性和芳烃收率。当Zn负载量为1.5%(质量分数)时,所制备的Zn-WC/HZSM-5催化剂芳构化活性最佳,芳烃收率达到36.18%。Zn的引入不仅改变了WC/HZSM-5表面的酸性分布,而且可以减少WC/HZSM-5催化剂的积炭量。     

Adsorption properties of methane on Mo and Pd–Ga loaded HZSM-5 at mild temperature

Methane adsorption on Mo/HZSM-5 and Pd–Ga/HZSM-5 was investigated by TPD. Even at 323 K, methane could adsorb on the catalysts. It dissociated transferred to the high hydrocarbons with temperature increase. The enough concentration of intermediates is necessary step for aromatics formation. The higher ability of hydrogenation over Pd–Ga/HZSM-5 than that over Mo/HZSM-5 was probably the reason for the rich in hydrogenation products and the lack of H₂.     

Synthesis of Mo/IM-5 catalyst and its catalytic behavior in methane non-oxidative aromatization

A Mo-modified catalyst, Mo-IM-5, was prepared for the non-oxidative aromatization of methane, and for comparison, Mo-ZSM-5 was also synthesized for the same reaction. The physical properties and acidities of the samples were characterized by XRD, SEM, BET and IR spectroscopy. Compared with Mo-ZSM-5, the Mo-IM-5 catalyst showed both a higher methane conversion and higher benzene selectivity. In addition, Mo-IM-5 was slightly more stable than Mo-ZSM-5. The catalytic behavior of Mo-IM-5 may be attributed to its unusual two-dimensional 10-member-ring channel system with the character of three-dimensional cavity. Furthermore, the effects of different Si/Al ratios, Mo loadings and temperatures on the catalytic performance of Mo-IM-5 were also investigated.     

Direct partial oxidation of methane over ZSM-5 catalyst: Zn-ZSM-5 catalyst studies

Extended studies on Zn-ZSM-5 catalyst for the production of liquid hydrocarbons in the direct partial oxidation (DPO) of CH₄ with O₂ are reported. Previously, it was reported that metal-containing ZSM-5 catalysts could produce C₅₊ hydrocarbons from pure CH₄/O₂ feeds without feed additives. Zn-ZSM-5 produced the highest C₅₊ yields of the catalysts tested. This work shows that the method of introducing Zn onto the catalyst, ion-exchange versus impregnation, does not significantly alter C₅₊ yields if low Zn content is maintained ( 0.4–0.5 wt%). Liquid hydrocarbon yields in this system doubled after 8 h on stream while overall C₂₊ yields increased by over 300%. Mechanistic implications of these findings are discussed. Finally, processing a natural gas feed over Zn-ZSM-5 gave higher C₅₊ yields over CH₄ feed but these yields were not improved over previously published results using HZSM-5.     

Characterization of surface carbon formed during the conversion of methane to benzene over Mo/H-ZSM-5 catalysts

During the conversion of methane to benzene in the absence of oxygen over a 2 wt% Mo/H-ZSM-5 catalyst at 700°C, three different types of surface carbon have been observed by X-ray photoelectron spectroscopy: adventitious or graphitic-like C (284.6 eV), carbidic-like C (282.7 eV), and hydrogen-poor sp-type C (283.2 eV), where the C 1s binding energies for the respective forms of carbon are given in parentheses. Pretreatment of the catalyst at 700°C in CO also resulted in a strong signal at 283.2 eV; thus, the species responsible for this signal appears to be different from the usual aromatic-type coke. The coke with dominantly sp hybridization is concentrated on the external surface of the zeolite and is responsible for the gradual deactivation of the catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interaction between ammonium heptamolybdate and NH4ZSM-5 zeolite: the location of Mo species and the acidity of Mo/HZSM-5

Mo/HZSM-5 catalysts show high reactivity and selectivity in the activation of methane without using oxidants. Mo/HZSM-5 catalysts with Mo loading ranging from 0 to 10% were prepared by impregnation with an aqueous solution of ammonium heptamolybdate (AHM). The samples were dried at 393 K, and then calcined at different temperatures for 4 h. The interaction between Mo species and NH₄ZSM-5 zeolite was characterized by FT-IR spectroscopy, differential thermal analysis (DTA) and temperature programmed decomposition (TPDE) and NH₃-TPD at different stages of catalyst preparation. The results showed that if Mo/HZSM-5 catalysts were calcined at a proper temperature, the Mo species will interact with acid sites (mainly with BrØnsted acid sites) and part of the Mo species will move into the channel. The Mo species in the form of small MoO₃ crystallites residing on the external surface and/or in the channel, and interacting with BrØnsted acid sites may be responsible for the methane activation. Strong interaction between Mo species and the skeleton of HZSM-5 will occur if the catalyst is calcined at 973 K. This may lead to the formation of MoO ₄ ^2– species, which is detrimental to methane activation.     

Study on attrition of spherical-shaped Mo/HZSM-5 catalyst for methane dehydro-aromatization in a gas-solid fluidized bed

As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,long-time rapid movement and chemical reaction.Existing evaluation methods for attrition resistance,such as ASTM D5757 and Jet Cup test,are targeted for fresh catalysts at ambient temperature,which cannot well reflect the real process.In this study,spherical-shaped Mo/HZSM-5 catalyst prepared by dipping and spray drying was placed in a self-made apparatus for attrition testing,in which the catalyst attrition under differ-ent system temperatures,running time and process factors was investigated with percent mass loss (PML),particle size-mass distribution (PSMD) and scanning electron microscope (SEM).Carbon deposition on the catalyst before and after activation,aromatization and regeneration was analyzed by thermogravimetry(TG),and the attrited catalysts were evaluated for methane dehydro-aromatization (MDA).The results show that the surface abrasion and body breakage of catalyst particles occur continuously,with the increase of system temperature and running time,and make the PML rise gradually.The process factors of activation,aromatization and regeneration can cause the catalyst attrition and carbon deposits,which broaden the PSMD in varying degrees,and the carbon-substances on catalysts greatly improve their attrition resistance at high temperature.Catalyst attrition has a certain influence on its catalytic performance,and the main reasons point to particle breakage and fine powder escape.     

Mo/HZSM-5分子筛催化合成乳酸酯的研究

利用Ｍｏ／ＨＺＳＭ－５分子筛催化剂,合成了六种乳酸酯,考察了催化剂用量、酸醇比、带水剂用量及反应时间等因素对反应的影响。结果表明,在适宜的反应条件下,乳酸酯的产率在８５％以上,且高碳醇的酯产率高于低碳醇的酯产率,正碳醇的酯产率高于仲碳醇的酯产率     

Performance of 3%Mo/ZSM‐5 catalyst in the presence of water during methane aromatization in supersonic jet expansion

The influence of water in the CH₄ feed on the performance of 3%Mo/ZSM‐5 catalyst during methane direct aromatization under supersonic jet expansion (SJE) condition was investigated. We observed that both surface Mo₂O_xC_y and β‐Mo₂C species are catalytically active for methane aromatization under SJE condition. The presence of water can promote the removal of surface carbon before the generation of aromatic‐type and/or graphitic carbon. In appropriate amount, water can improve the stability of surface Mo₂O_xC_y, and hence resulting in better catalytic performance. The study provided valuable information relevant to the direct utilization of methane hydrate. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

锌和磷含量对Zn-P/HZSM-5催化剂芳构化性能的影响

在反应温度430 ℃、压力0.1 MPa、液时空速1 h－1条件下,进行催化裂化汽油中间馏分（75～120 ℃）的芳构化反应,考察了锌和磷含量对催化剂性能的影响。实验结果表明,当锌和磷质量分数分别为2％和4％时,改性催化剂芳构化活性及芳烃选择性最佳,其烯烃转化率、芳烃含量和芳烃收率分别为94.53 ％、68.8 ％ 和51.74 ％。     

甲烷常压非催化部分氧化制合成气研究

考察了常压下甲烷非催化部分氧化制合成气过程中,甲烷转化率、气体产物产率以及积炭率随反应器温度、进气配比、原料气流量变化的影响。通过考察反应器温度对制备合成气过程的影响结果,分析了甲烷非催化部分氧化制合成气过程的反应机理。