不同硅铝比HZSM-5分子筛对合成气一步法制二甲醚的影响

采用固定床高压反应装置,以工业用（CuO／ZnO／Al2O3）作为甲醇合成催化剂,四种不同硅铝比（硅铝比为25、38、50和150）的HZSM-5作为甲醇脱水催化剂,二者机械混合制备出一步法合成二甲醚双功能催化剂。考察了催化剂中脱水组分（HZSM-5分子筛）的硅铝比对二甲醚合成反应的影响,并通过BET、XRD和NH,-TPD等手段对催化剂进行表征。结果表明,一步法合成二甲醚催化剂中脱水组分HZSM-5的最佳的硅铝比为50。     

Nafion/HZSM-5有相-无机复合质子交换膜的制备与性能研究

通过重铸的方法制备了Nafion/HZSM-5有机-无机复合质子交换膜,研究了添加HZSM-5纳米沸石分子筛颗粒对Nafion膜的结构、水吸收、质子传导率、热稳定性和化学稳定性的影响.与纯的重铸Nafion膜相比,含有5%(质量分数)HZSM-5分子筛的Nafion/HZSM-5复合膜具有更高的质子传导率,当HZSM-5的质量分数高于5%时,复合膜的质子电导率随着HZSM-5含量的增加有所降低,而Nafion/HZSM-5复合膜的水吸收率在HZSM-5质量分数为7.5%时最高,Nafion/HTSM-5复合膜的降解温度也高于纯的重铸的Nafion膜,Nafion/HZSM-5复合膜性能的提高可能与HZSM-5的酸性和特殊的孔道结构有关.     

HZSM-5对生物质合成气一步法合成LPG的影响

研究了MeLi与HZSM-5型分子筛不同质量配比混合制备的合成液化石油气(LPG)催化剂的性能,评价了不同硅铝比(硅铝摩尔比为25、38、50)HZSM-5型分子筛酸性对LPG合成的影响,结果表明,MeLi与HTZSM-5型分子筛质量比在2∶1时对合成LPG最佳,随着分子筛硅铝摩尔比的降低,分子筛的酸性增强,CO单程转化率提高.HZSM-5型分子筛在合成LPG过程中,硅铝比为38时最佳,空速在1 500 h->时,CO转化率为84.87%,碳氢化合物产物中C3 C4所占比例(摩尔分数)最高,达到58.21%.通过计算,每吨干基生物质气化得到合成气,经合成单程转化可得到0.0786 t LPG,联产电力607 kWh.     

Synthesis of ZSM-5/SAPO-11 composite and its application in FCC gasoline hydro-upgrading catalyst

This article describes the synthesis, characterization and application of a novel aluminosilicate/silicoaluminophosphate composite zeolite ZSM-5/SAPO-11. The composite was synthesized by the in situ overgrowth of SAPO-11 on ZSM-5 and was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transformed infrared (FT-IR) spectrometry, N₂ adsorption and infrared spectroscopy of adsorbed pyridine. The results were compared with those of the mechanical mixture composed of individual ZSM-5 and SAPO-11. In the mechanical mixture, the ZSM-5 phase was morphologically separate from the SAPO-11 phase, while the ZSM-5/SAPO-11 composite existed in a form of a core-shell structure, with the ZSM-5 phase as the core and the SAPO-11 phase as the shell. Compared with the mechanical mixture, the composite had more mesopores and moderate acidity distribution, which could accelerate the diffusion of substances and enhance the synergetic effect between Brönsted and Lewis acids. The comparison of the catalytic performances of the mechanical mixture and the composite-based Ni–Mo catalysts for FCC gasoline hydro-upgrading showed that, due to the above advantages of the composite, the corresponding catalyst yielded improved gasoline research octane number, high liquid yield, good desulfurization activity and lower coke amount and thus could be considered as a potential catalyst system for hydro-upgrading FCC gasoline.     

Fischer-Tropsch synthesis and the generation of DME in situ

Ternary physical mixtures comprised a Fischer-Tropsch catalyst, a methanol synthesis catalyst and a zeolite employed in the hydrocarbon synthesis from syngas. Two Fe-based catalysts (i.e., one promoted by K and the other by Ru), two HY zeolites with different acidities, a commercial HZSM-5 and Cu/ZnO/Al₂O₃ (methanol synthesis catalyst) were used in these systems. The main products obtained were dimethyl ether, methanol and hydrocarbons. First of all, it was observed that by adding Cu/ZnO/Al₂O₃ catalyst to a binary physical mixture comprised of a Fischer-Tropsch catalyst and HZSM-5, the CO conversion increases more than 20 times. Second, during the reaction transient period the dimethyl ether selectivity decreases as the conversion increases. Third, the hydrocarbons synthesized followed the ASF distribution in the C₁-C₁₂ range and finally, it was also verified that the Y zeolites and the Fischer-Tropsch synthesis catalyst promoted by Ru generated the most active physical mixtures. The results showed that the role of zeolites in the ternary physical mixture is only associated with the dimethyl ether synthesis. The following reaction pathway was suggested: first, methanol is synthesized from syngas using Cu/ZnO/Al₂O₃ catalyst; after that, this alcohol is dehydrated by an acid catalyst generating DME; and lastly, DME initiates Fischer-Tropsch synthesis, which is then propagated by CO.     

合成气一步法5000t/a二甲醚管式反应器设计

应用实验所得动力学数据,建立管式固定床反应器的一维数学模型。通过计算典型工况下5000t/a二甲醚反应器,得到了反应器的工艺与设备设计参数。     

Methane and ethane activation without adding oxygen: promotional effect of W in Mo-W/HZSM-5

The conversions of methane and ethane over Mo/HZSM-5 and W/HZSM-5 catalysts are compared. A reaction model for hydrocarbon formation over Mo/HZSM-5 catalysts is proposed, which involves heterolytic splitting of methane and a molybdenum-carbene intermediate. Ethene is shown to be the initial product of methane conversion, and it undergoes further reaction to form aromatics in a solid acid environment. The promotional effect of addition of tungsten in the Mo-W/HZSM-5 catalyst in methane conversion reaction suggests the formation of Mo-W mixed oxide. The product selectivity patterns of Mo/HZSM-5 and W/HZSM-5 catalysts in ethane conversion reaction are consistent with a dual-path model involving dehydrogenation and cracking (or hydrogenolysis) of ethane. The rates of both these reactions over Mo/HZSM-5 are higher than over W/HZSM-5.     

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.     

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.     

Conversion of canola oil to various hydrocarbons over Pt/HZSM-5 bifunctional catalyst

Canola oil conversion was studied at atmospheric pressure over Pt/HZSM-5 catalyst (0.5 mass% Pt) in a fixed bed micro-reactor. The operating conditions were: temperature range of 400?500°C, weight hourly space velocity (WHSV) of 1.8 and 3.6 h^?1 and steam/oil ratio of 4. The objective was to optimize the amount of gasoline range hydrocarbons in the organic liquid product (OLP) and the selectivity towards olefins and isohydrocarbons in the gas product. The gas yields varied between 22–65 mass% and were higher in the presence of steam compared to the operation without steam. The olefin/paraffin mass ratio of C₂-C₄ hydrocarbon gases varied between 0.31–0.79. The isohydrocarbons/n-hydrocarbons ratio was higher with Pt/HZSM-5 (1.6–4.8) compared with pure HZSM-5 catalyst (0.2–1.0). The OLP yields with Pt/HZSM-5 (20–55 mass% of canola oil) were slightly lower compared to HZSM-5 (40–63 mass% of canola oil) under similar conditions. The major components of OLP were aliphatic and aromatic hydrocarbons. A scheme postulating the reaction pathways for the conversion of canola oil over Pt/HZSM-5 catalyst is also presented.     

Gasoline-range hydrocarbon synthesis over Co/SiO2/HZSM-5 catalyst with CO2-containing syngas

Selective synthesis of gasoline-range hydrocarbons (C₅-C₁₂) was investigated in a fixed-bed micro reactor using two series of CO₂-containing syngas with various mole CO₂/(CO + CO₂) and H₂/(CO + CO₂) ratios, where Fischer-Tropsch synthesis(FTS) and in situ hydrocracking/hydroisomerization were performed over bifunctional Co/SiO₂/HZSM-5 catalyst. CO₂ was converted at 0.15-0.55 of CO₂/(CO + CO₂) ratio under H₂-rich condition (H₂/(CO + CO₂) = 2.0), highest conversion of 20.3% at 0.42. Further increasing CO₂ content decreased CO₂ conversion and quite amount of CO₂ acted as diluting component. For the syngas with low H₂ content or H₂/(CO + CO₂) ratio(< 1.85, H₂/CO = 2.0), the competitive adsorption of CO, H₂ and CO₂ resulted in low CO, CO₂ and total carbon conversion, which was 57.9%, 12.7% and 31.4% respectively at 0.74 of H₂/(CO + CO₂) ratio(H₂/CO/CO₂/N₂ = 40.8/20.4/34.8/4). FTS results indicated that high H₂ content and proper H₂/(CO + CO₂) ratio were favorable for the conversion of CO₂-containing syngas. More than 45% selectivity to gasoline-range hydrocarbons including isoparaffins was obtained under the two series of syngas. It was also tested that the catalytic activity of Co/SiO₂/HZSM-5 kept stable under CO₂-containing syngas(< 7.5%). And the quick catalytic deactivation under high CO₂ containing syngas(H₂/CO/CO₂/N₂ = 45.3/23.2/27.1/3.06) was due to carbon deposition and pore blockage by heavy hydrocarbon, tested by thermal gravimetry, N₂ physisorption and scanning electron microscopy(SEM).     

正庚烷在Pt/HZSM-5上临氢芳构化反应研究

程序升温还原法(TPR)制备了Pt/HZSM-5催化剂,并进行了XRD表征。采用正庚烷为模型化合物,在小型连续固定床反应装置上考察了改性HZSM-5分子筛在催化裂化条件下的芳构化反应性能。结果表明,Pt/HZSM-5催化剂具有较高的活性和稳定性。在反应温度450℃、压力1.5MPa、体积空速2.0h-1、氢油比800:1的条件下,正庚烷的转化率达到99.3%,液相产品中芳烃质量分数为64.45%,液相收率为58.45%。     

A Transient Behaviour in the Initial Production of Aromatic Compounds from Methane Catalyzed by Mo/HZSM-5

The production of aromatic compounds directly from methane using catalysts based on zeolite HZSM-5 impregnated with molybdenum was investigated using a flow reactor at 750 °C. Main products were benzene and naphthalene as well as toluene and others like azulene in smaller amounts. Naphthalene appeared after benzene following an induction period suggesting a consecutive reaction path. A transient behavior in the production of naphthalene was observed along the time on stream, being benzene practically the only product at the steady state. The transient behavior disappeared when increasing contact time, which produced more naphthalene at the expense of benzene.     

氧化镁改性HZSM-5分子筛的酸性及在合成气直接制二甲醚反应中的应用——镁前驱体的影响

以乙酸镁为前驱体采用浸渍法制备了一系列不同氧化镁(MgO)含量(0%～20%)的镁改性HZSM-5分子筛,并采用X射线衍射(XRD)、N2吸附、X射线光电子能谱(XPS)、氨程序升温脱附(NH3-TPD)和吡啶吸附红外光谱(Py-IR)方法对其结构和酸性进行了表征.在连续流动加压固定床反应器中及温度260℃、压力4 Mpa和气体空速1500 mL·gcat·h)-1条件下,考察了以上述HZSM-5分子筛为甲醇脱水活性组分与铜基甲醇合成活性组分(CuO-ZnO-Al2O3)所组成的双功能催化剂对合成气直接制二甲醚反应的催化性能.结果表明,HZSM-5分子筛经适量的MgO改性后,产物中二甲醚的选择性由49.1%提高到68%以上,而二氧化碳和烃类副产物的选择性则分别由37.1%和9.3%降低到27%和0.1%以下.烃类和二氧化碳副产物减少的原因是MgO改性降低了HZSM-5分子筛强酸中心的酸量,尤其是减少了强Br?nsted酸的酸量.另外,与以硝酸镁为前驱体制备的MgO/HZSM-5不同,MgO在较大的范围(2.5%～20%)内对其催化性能几乎无影响.     

Production of gasoline range hydrocarbons from catalytic reaction of methane in the presence of ethylene over W/HZSM-5

The catalytic conversion of a methane and ethylene mixture to gasoline range hydrocarbons has been studied over W/HZSM-5 catalyst. The effect of process variables, such as temperature, percentage of volume of ethylene in the methane stream and catalyst loading on the distribution of hydrocarbons was studied. The reaction was conducted in a fixed-bed quartz-micro reactor in the temperature range of 300–500 °C using percentage of volume of ethylene in methane stream between 25 and 75% and catalyst loading of 0.2–0.4 g. The catalyst showed good catalytic performance yielding hydrocarbons consisting of gaseous products along with gasoline range liquid products. The mixed feed stream can be converted to higher hydrocarbons containing a high-liquid gasoline product selectivity (>42%). Non-aromatics C₅–C₁₀ hydrocarbons selectivity in the range of 12–53% was observed at the operating conditions studied. Design of experiment was employed to determine the optimum conditions for maximum liquid hydrocarbon products. The distribution of the gasoline range hydrocarbons (C₅–C₁₀ non-aromatics and aromatics hydrocarbons) was also determined for the optimum conditions.     

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     

浆态床合成气合成二甲醚的工艺研究

考察了反应温度、反应压力、进料空速对浆态床合成二甲醚反应过程的影响,结果表明,在245～300℃范围内,随着反应温度的升高,一氧化碳转化率、二甲醚选择性和时空收率逐渐增加,在265℃时达到最大值后开始下降;在3.0～5.0MPa范围内,随压力的升高,一氧化碳转化率、二甲醚选择性和时空收率逐渐增加;在700～2500h-1范围内,一氧化碳转化率、二甲醚选择性随空速的增加而逐渐减小,空速以1200h-1为宜。     

Characterization and catalytic application of MnCl2 modified HZSM-5 zeolites in synthesis of aromatics from syngas via dimethyl ether

The conversion of syngas to aromatics via dimethyl ether was investigated over MnCl₂ modified HZSM-5 zeolites. The results demonstrated that 2%MnCl₂ modified HZSM-5 (SiO₂/Al₂O₃ = 38) exhibited higher p-xylene selectivity than other catalysts and further decreased 1,2,4,5-tetramethylbenzene selectivity. The CO conversion was obviously increased after 5%MnCl₂ modification to HZSM-5. The catalysts were characterized by XRD, BET, XPS, FT-IR, NH₃-TPD, SEM, element analysis and O₂-TPO. The loading amount of MnCl₂ affected the adsorption and reaction of DME molecules on zeolites. Appropriate amount of MnCl₂ introduction could adjust the acidity and pore volume of HZSM-5 to increase p-xylene selectivity and CO conversion.     

Deactivation and regeneration of hybrid catalysts in the single-step synthesis of dimethyl ether from syngas and CO2

Synthesis of dimethyl ether (DME) has been studied in a single reaction step, from H₂ + CO and H₂ + CO₂, in a fixed bed reactor on CuO-ZnO-Al₂O₃/γ-Al₂O₃ and CuO-ZnO-Al₂O₃/NaHZSM-5 hybrid catalysts. It has been proven that water content in the reaction medium (which is higher when CO₂ is fed) contributes to efficiently decreasing deactivation by coke in both catalysts and, consequently, when water is in the feed deactivation is insignificant for 30 h reaction. Nevertheless, water also decreases the activity of γ-Al₂O₃ acid function, due to its high adsorption capacity on the acid sites. Due to its importance in the viability of the industrial process, a study has been carried on the regeneration of both catalysts by coke combustion under controlled conditions (in order to avoid CuO sintering). For this study, the catalysts have been used under severe deactivation conditions. It has been proven that γ-Al₂O₃ does not have a suitable hydrothermal stability and that CuO-ZnO-Al₂O₃/NaHZSM-5 catalyst has an excellent performance and is suitable for using it in uninterrupted reaction–regeneration cycles.     

Study of the interaction between components in hybrid CuZnAl/HZSM-5 catalysts and its impact in the syngas-to-DME reaction

Hybrid CuZnAl(CZA)/HZSM-5 catalysts were prepared by three mixing methods in order to analyze the possible existence of interactions between components and their impact in the STD process, namely: (a) grinding of powders prior to pelletizing (grinding method), (b) slurrying the two solids in water followed by drying and pelletizing (slurry method), and (c) physical mixture of pre-pelletized components. The materials were characterized by ICP-OES, XRD, N₂ physisorption, H₂-TPR, ²⁷Al MAS NMR, FTIR-pyridine, and EPR spectroscopy. Detrimental interactions producing a drastic reduction in the amount of available zeolitic Brønsted acid sites were observed for the hybrids prepared by slurry and grinding methods. Such interactions involved, on one hand, the partial blockage of micropores by CZA particles and, on the other hand, an inter-cationic exchange of Cu²⁺ (and possibly also Zn²⁺) species. The presence of isolated Cu²⁺ cations occupying exchange positions in the HZSM-5 zeolite was unambiguously evidenced by EPR spectroscopy. The decrease in Brønsted acidity significantly reduced the activity of the zeolite for dehydrating methanol leading to a much lower efficiency of the corresponding hybrids for DME synthesis at typical STD conditions as compared to the catalyst obtained by simple mixture of pre-pelletized components.