SiO2/HZSM-5对钴基催化剂费托合成汽油烃类的影响

以硅胶和HZSM-5分子筛为载体制备了钴基催化剂,在固定床上进行费托合成反应.考察了中孔硅胶和微孔HZSM-5的结合形式及载体和钴粒子间相互作用等对汽油类碳氢化合物合成的影响.结果表明催化剂具有一定的微孔和中孔结构对汽油类碳氢化合物合成有利,当硅胶中孔孔径适当时,HZSM-5均匀分布在大比表面硅胶上,使得催化剂同时具有中孔和微孔结构,具有较强的CO加氢反应能力和二次反应能力.实验中CO转换率达到83%,汽油类碳氢化合物选择性高达55%,其中异构烷烃选择性在10%以上.     

正己烷异构化催化剂Pd/HZSM-5的研究

通过临氢微型反应器中催化剂评价实验,对Pd质量分数为0.1％、0.2％、0.3％、0.4％和0.5％ 的Pd/HZSM-5催化剂进行了评价,其裂解率分别为4.480 6%、3.481 7%、4.188 4%、4.585 8%和2.818 2%,裂解率较高。在考察的范围内,催化剂的活性、异构化率均随着Pd质量分数的增加而略有上升;Pd质量分数在0.30％～0.50％时催化剂稳定性良好,Pd含量过低催化剂较易失活,催化剂的选择性较低。     

ZnxZr/HZSM-5 as efficient catalysts for alkylation of benzene with carbon dioxide

Alkylation of benzene with carbon dioxide and hydrogen to produce toluene and xylene could increase the added-value of surplus benzene as well as relieve environmental problems like green-house effect. In this work, the alkylation benzene with carbon dioxide and hydrogen reaction was proceeded by using the mixture of zinc-zirconium oxide and HZSM-5 as bifunctional catalyst. The equivalent of Zn/Zr = 1 displays the best catalytic performance at 425 °C and 3.0 MPa, and benzene conversion reaches 42.9% with a selectivity of 90% towards toluene and xylene. Moreover, the carbon dioxide conversion achieves 23.3% and the carbon monoxide selectivity is lower than 35%, indicating that more than 50% carbon dioxide has been effectively incorporated into the target product, which is the best result as far as we know. Combined with characterizations, it indicated that the Zn and Zr formed a solid solution under specific conditions (Zn/Zr = 1). The as-formed solid solution not only possesses a high surface area but also provides a large amount of oxygen vacancies. Additionally, the bifunctional catalyst has excellent stabilities that could keep operating without deactivation for at least 80 h. This work provides promising industrial applications for the upgrading of aromatics.     

Hydrothermal stability of HZSM-5 catalysts modified with Ni for the transformation of bioethanol into hydrocarbons

The hydrothermal stability of catalysts prepared from HZSM-5 zeolites doped with Ni (by impregnation) has been studied in the transformation of bioethanol into hydrocarbons, in order to remove the main barrier for the use of HZSM-5 zeolite catalysts in this process, which is the irreversible deactivation by dealumination of the zeolite above 400 °C with water in the reaction medium. The main effect of doping is the attenuation of the zeolite acid strength from 135 to 125 kJ (mol of NH₃)⁻¹ for a Ni content of 1 wt.%. The catalysts maintain a high level of activity and a high selectivity of propene and butenes, and Ni doping significantly attenuates irreversible deactivation of the catalyst by dealumination of the zeolite. The zeolite catalyst doped with 1 wt.% of Ni maintains its kinetic behaviour in reaction-regeneration cycles when the reaction step is carried out at 500 °C and with 5 wt.% of water in the feed. This catalyst allows operating at 400 °C without irreversible deactivation with bioethanol containing 75 wt.% of water.     

Transformation of methanol to gasoline range hydrocarbons using HZSM-5 catalysts impregnated with copper oxide

Various CuO/HZSM-5 catalysts were studied in a fixed bed reactor for the conversion of methanol to gasoline range hydrocarbons at 673 K and at one atmospheric pressure. The catalysts were prepared by wet impregnation technique. Copper oxide loading over HZSM-5 (Si/Al=45) catalyst was studied in the range of 0 to 9 wt%. XRD, BET surface area, metal oxide content, scanning electron microscopy (SEM) and thermogravimetric (TGA) techniques were used to characterize the catalysts. Higher yield of gasoline range hydrocarbons (C₅-C₁₂) was obtained with increased weight % of CuO over HZSM. Effect of run time on the hydrocarbon yields and methanol conversion was also investigated. The activity of the catalyst decreased progressively with time on-stream. Hydrocarbon products’ yield also decreased with the increase in wt% of CuO. Relatively lower coke deposition over HZSM-5 catalysts was observed compared to CuO impregnated HZSM-5 catalyst.     

Core-shell structured HZSM-5@mesoSiO2 catalysts with tunable shell thickness for efficient n-butane catalytic cracking

A series of core-shell HZSM-5@mesoSiO₂ with tunable shell thickness from 10 to 70 nm was prepared and studied for n-butane catalytic cracking. With introducing of SiO₂ shell, the catalytic performance of HZSM-5@mesoSiO₂ was largely enhanced, and n-butane conversion rate per Al site reached to 2.43 min⁻¹ over HZSM-5@mesoSiO₂(1:4) at 675°C which is nearly twice to that of HZSM-5 (1.34 min⁻¹). The diffusion property of n-butane over as-prepared sample was quantified by measuring the diffusional time constants using zero length column chromatography technique (ZLC). Combining with chemical reaction kinetic analysis, the quantitative relationship between diffusion property and catalytic performance was effectively established for the first time in n-butane catalytic cracking. Positive linear correlation between diffusional time constant (D/R²) and n-butane conversion rate per Al site could be found, which confirms that diffusion enhancement by hierarchical structure is an effective strategy to improve the activity of HZSM-5 in catalytic cracking.     

Cordierite monolith supported perovskite-type oxides — catalysts for the total oxidation of chlorinated hydrocarbons

The catalytic behaviour of LaMnO₃, LaCoO₃ and (La_0.84Sr_0.16)(Mn_0.67Co_0.33)O₃ perovskites supported on cordierite monoliths was studied in the total oxidation of chlorinated hydrocarbons (CHC). By-products (higher chlorinated hydrocarbons, lower molecular coupling and cracking products) were formed in the low temperature range depending on the kind and concentration of CHC in the feed and the reaction conditions. The preparation method (impregnation or coating) influences catalytic activity and by-product formation. Addition of water, methane or propane to the feed diminishes the by-product formation significantly. In the case of monolith supported LaCoO₃ perovskite, an irreversible catalyst deactivation was observed.     

Yield of gasoline-range hydrocarbons as a function of uniform ZSM-5 crystal size

Uniform ZSM-5 nanocrystals were synthesized by a single-templating procedure. The samples were then characterized by a variety of physical techniques such as XRD, SEM, BET, ICP and TPD. The dehydration of methanol over synthesized ZSM-5 zeolite was studied in a fixed-bed continuous flow reactor at 370 °C and WHSV of 2.6 gg⁻¹ h under ambient pressure. The effect of crystal size of zeolite catalysts on product distribution in methanol dehydration reaction was investigated. Good correlation was observed between catalytic performance, product distribution and size of ZSM-5 crystals. It was found that the decrease in crystal size significantly influences light olefins (ethylene and propylene) and paraffins (C₁–C₄) selectivity in methanol dehydration reaction. Furthermore, nanocrystal ZSM-5 showed long-term catalytic stability compared with conventional ZSM-5 provided that the reaction activity is strongly dependent on the crystal size in methanol dehydration process. The results indicated that crystal size significantly affects the catalyst lifetime and hydrocarbon distributions in product stream. Based on the obtained results, it is concluded that the use of uniform ZSM-5 nanocrystals improves the yield of propylene and alkyl aromatics in methanol conversion reaction at mild conditions.     

SHS-produced intermetallides as catalysts for deep oxidation of carbon monoxide and hydrocarbons

Investigated was the catalytic activity of multicomponent metal catalysts prepared by alkaline leaching of SHS-produced (NiAl₃) _x (CoAl₃) _y and (NiAl₃) _x (CoAl₃) _y (MnAl₃) _z intermetallides in deep oxidation of carbon monoxide and hydrocarbons. The morphology and composition of starting and leached intermetallides were characterized by SEM, while the specific surface of the catalysts was determined by BET method. The above preparation technique can be expected to open up a new route to synthesis of high-efficiency polymetallic catalysts for deep oxidation of CO and hydrocarbons.     

Comparative study of IPTBE synthesis on HZSM-5 and ion-exchange resin catalysts

The title ether was synthesized using a batch reactor at 70–90°C and 1.6 MPa. The ion-exchange resins Amberlyst 15, Amberlyst 35 and Purolite CT275, and HZSM-5 zeolites with a SiO₂/Al₂O₃ ratio between 28 and 120 were used as catalysts. IPTBE synthesis rapidly reaches chemical equilibrium in the presence of resins with selectivities of 95–97%, diisobutene being the main byproduct. HZSM-5 zeolites are less active and selective than resin catalysts. Resins, especially Amberlyst 35, are suitable catalysts for obtaining IPTBE industrially.     

Sialon-supported catalysts for deep oxidation of carbon monoxide and hydrocarbons

Catalysts supported on a new class of supports—β-Sialons Si_{6 ? z} Al _z O _z N_{8 ? z} (z = 1, 3, 4) modified with transition-metal oxides—were synthesized and tested in the complete and partial oxidation of hydrocarbons and CO. These Sialons were prepared by self-propagating high-temperature synthesis (SHS). Catalytic activity in the test reactions appeared in systems that contain unary, binary, or ternary mixtures of metal oxides of the second half of the 3d row. Cobalt oxide-based catalysts showed the highest activity. Methods were proposed for activating Sialon supports with a considerable enhancement of the activity of a supported catalyst. More precise investigative tools are required for refining new data and understanding the nature and operation mechanism of Sialons. On account of their high thermal stability and wear resistance, Sialon-supported catalysts are proposed for use in deep oxidation processes in abrasive and acid solutions and at elevated temperatures.     

Metalloporphyrins encapsulated mesoporous molecular sieves as efficient heterogeneous catalysts for oxidation of cyclohexene with iodosylbenzene

The cationic Fe, Mn or VO porphyrins were encapsulated in Si, Al, Ti and V-MCM-41. The catalytic activity was investigated for the oxidation of cyclohexene with iodosylbenzene (PhIO) as oxidant. Manganese porphyrin supported catalysts produces epoxide as major products whereas iron and vanadyl porphyrins gave allylic oxidation products as major constituents. The results obtained clearly shows that the selectivity of various products depends not only on the nature of the support materials but also on the combined effects of metalloporphyrins and the supports. The recyclability of the heterogeneous catalysts was also investigated. The decrease in catalytic activity and leaching of active centers were observed when porphyrins were supported on Si-MCM-41.     

Production of aromatic hydrocarbons by co-cracking of bio-oil and ethanol over Ga2O3/HZSM-5 catalysts

The catalytic cracking of bio-oil is important to produce aromatic hydrocarbons, which can partially replace gasoline or diesel to greatly reduce carbon emissions from transportation. To further promote the formation of aromatic hydrocarbons, this work studied the effects of the preparation method and the acid strength of Ga₂O₃/HZSM-5 on catalytic cracking of the bio-oil distilled fraction systematically. The preparation method of Ga₂O₃/HZSM-5 had an important effect on its catalytic activity: the Ga₂O₃/HZSM-5 prepared by physical mixing showed the low dispersion of active phases and poor pore structure, resulting in its insufficient activity and severe coke deposition; the Ga₂O₃/HZSM-5 prepared by precipitation exhibited the higher activity, while many polycyclic aromatic hydrocarbons unfavorable for the subsequent utilization were in the oil phase; the Ga₂O₃/HZSM-5 prepared by impregnation showed the highest activity and 35.5% (mass) selectivity of the oil phase, including 80.3% monocyclic aromatic hydrocarbons and 12.0% polycyclic aromatic hydrocarbons. The Brønsted acidity of Ga₂O₃/HZSM-5 decreased with Si/Al ratio, leading to the decline in reactant conversion, oil phase selectivity and quality. Meanwhile, the polymerization between monocyclic aromatic hydrocarbons and oxygenates was promoted to produce many polycyclic aromatic hydrocarbons and even coke, causing catalyst deactivation.     

Effect of Ru addition to Co/SiO2/HZSM-5 catalysts on Fischer–Tropsch synthesis of gasoline-range hydrocarbons

Microporous HZSM-5 zeolite and mesoporous SiO₂ supported Ru–Co catalysts of various Ru adding amounts were prepared and evaluated for Fischer–Tropsch synthesis (FTS) of gasoline-range hydrocarbons (C₅–C₁₂). The tailor-made Ru–Co/SiO₂/HZSM-5 catalysts possessed both micro- and mesopores, which accelerated hydrocracking/hydroisomerization of long-chain products and provided quick mass transfer channels respectively during FTS. In the same time, Ru increased Co reduction degree by hydrogen spillover, thus CO conversion of 62.8% and gasoline-range hydrocarbon selectivity of 47%, including more than 14% isoparaffins, were achieved simultaneously when Ru content was optimized at 1 wt% in Ru–Co/SiO₂/HZSM-5 catalyst.     

铝源对合成ZSM-5分子筛晶粒大小及形貌的影响

分别采用偏铝酸钠、硫酸铝、异丙醇铝为铝源,四丙基氢氧化铵为模板剂,用水热合成法制备了不同晶粒大小及不同形貌的ZSM-5分子筛.通过XRD、SEM等表征手段对各种锚源合成的分子筛结晶度、晶粒大小及形貌进行了对比分析.结果表明,以偏铝酸钠和异丙醇铝为铝源合成的ZSM-5分子筛晶粒较小,形貌趋于球形,且化学硅铝比与晶化前驱体的硅铝比基本一致;而以硫酸铝为铝源合成的ZSM-5分子筛硅铝比低于投料硅铝比,且晶粒较大.     

非临氢条件下流化催化裂化汽油降烯烃芳构化HZSM-5催化性能的研究

在非临氢条件下采用HZSM-5作为催化剂活性组元,研究了流化催化裂化(FCC)汽油芳构化降烯烃的反应性能。研究结果表明HZSM-5含量和其硅铝比对芳构化降烯烃反应具有重要影响,质量分数为30%以及硅铝摩尔比为58的HZSM-5催化剂的降烯烃和芳构化性能最佳,反映了其酸催化性能的适当的总酸量和合理的酸强度分布。反应温度和空速等主要工艺条件的研究结果表明,常压下反应温度以400℃左右为宜,空速可根据对烯烃和芳烃含量的限值在4~6 h-1内调整。FCC汽油经处理后的产物汽油烯烃体积分数可降低至8%~18%,相应的芳烃体积分数为42%~35%,道路法辛烷值不降低。     

Heterogeneous amino acid-based tungstophosphoric acids as efficient and recyclable catalysts for selective oxidation of benzyl alcohol

A series of organic-inorganic composite catalysts, prepared by modifying tungstophosphoric acid (TPA; H₃PW₁₂O₄₀) with different amino acids such as phenylalanine (Phe), alanine (Ala), and glycine (Gly) were synthesized. The physicochemical and acidic properties of these (MH) _x H_3?x PW₁₂O₄₀ (M=Phe, Ala, and Gly; x=1–3) composite materials were characterized by a variety of different analytical and spectroscopic techniques, namely TGA, XRD, FT-IR, XPS, and NMR, and exploited as heterogeneous catalysts for selective oxidation of benzyl alcohol (BzOH) with hydrogen peroxide (H₂O₂). Among them, the [PheH]H₂PW₁₂O₄₀ catalyst exhibited the best oxidative activity with an excellent BzOH conversion of 99.0% and a desirable benzaldehyde (BzH) selectivity of 99.6%. Further kinetic studies and model analysis by response surface methodology (RSM) revealed that the oxidation of BzOH with H₂O₂ follows a second-order reaction with an activation energy of 56.7 kJ·mol^?1 under optimized experimental variables: BzOH/H₂O₂ molar ratio=1 : 1.5 mol/mol, amount of catalyst=6.1 wt%, reaction time (x₃)=3.8 h, and amount of water (x₄)=30.2 mL.     

Catalytic performance and characterization of Ni-doped HZSM-5 catalysts for selective trimerization of n-butene

A series of Ni-doped HZSM-5 catalysts were prepared and the catalytic performance of these catalysts in n-butene trimerization was investigated. The Ni-loading, the Si/Al ratio of HZSM-5 and the reaction conditions (temperature, pressure and WHSV) played great influences on the catalytic performance of these catalysts in the reaction. 77.5 wt.% conversion of n-butene and 50.5 wt.% selectivity of trimers as well as 19.6 × 10^? 2 g_trimers/(g_cat h) yield of trimers were obtained on 1NiHZSM-5(320) catalyst up to 148 h at 420 °C, WHSV = 2 h^? 1 and 1.0 MPa. In addition, the physicochemical properties of these catalysts were comparatively characterized by powder X-ray diffraction (XRD), N₂ isothermal adsorption–desorption, infrared red spectroscopy (IR) and pyridine adsorbed infrared red spectroscopy (Py-IR) techniques. The doping of Ni into HZSM-5(320) modified the specific surface area and the acidity of these catalysts, which in turn affected the catalytic performance of these catalysts in n-butene trimerization. The acidic amount and the ratio of Lewis/Brönsted acid sites (L/B) on the external surface of these catalysts were close relative to the catalytic performance of these catalysts. 1NiHZSM-5(320) catalyst showed the highest catalytic performance in n-butene trimersization among the investigated catalysts because it had the proper acidic amount and the proper L/B ratio on its external surface.     

烃类异构化小粒径、多级孔SAPO-11分子筛催化剂研究进展

由于小粒径、多级孔或兼具小粒径与多级孔结构的SAPO-11分子筛能够显著提高SAPO-11分子筛催化剂在烃类加氢异构化中的活性和选择性,近年来已成为烃类异构化催化剂研究的热点。本文按照SAPO-11分子筛的制备方法进行分类,系统介绍了小粒径、多级孔和兼具小粒径与多级孔结构的SAPO-11分子筛的制备及其临氢异构化性能,指出在今后的研究中,研究开发新的绿色高效合成方法,降低合成成本和减少环境污染是小粒径或（和）多级孔SAPO-11分子筛催化剂实现工业化应用亟待解决的突出问题和研究方向。     

Surfactant-stabilized PtRu colloidal catalysts with good control of composition and size for methanol oxidation

Well-dispersed PtRu/C catalysts were prepared by supporting surfactant-stabilized PtRu hydrosol on carbon followed by a heat-treatment at elevated temperature. The effect of the synthesis conditions and the heat-treatment on the composition and electrcatalytic properties of PtRu/C towards methanol oxidation was systematically investigated. It was found that the pH environment and the reaction temperature could greatly affect the final compositions of Pt and Ru in the PtRu catalysts. Moreover, after a post-heat-treatment process, the electrocatalytic activity of PtRu colloidal catalysts can be much improved, the enhancement of which can be largely explained by the improved alloying formation and the removal of surfactant from catalyst demonstrated by the XRD and XPS analyses, respectively.