Al-MCM-41分子筛对多环烃的催化异构化性能

采用室温法合成了Al-MCM-41分子筛,采用XRD、FT-IR和表面测定仪等方法表征了Al-MCM-41分子筛的结构。以多环烃endo-TCD（桥式四氢双环戊二烯）异构化反应为例考察了不同铝硅物质的量比的Al-MCM-41分子筛催化异构化性能,在此基础上研究了表面负载无机酸及贵金属Pt的促进作用。结果表明,Al-MCM-41分子筛对endo-TCD具有良好的催化异构化作用,无机酸的负载对催化剂活性和提高金刚烷收率具有一定促进作用,而采用化学还原法负载Pt则未达到预期目的。     

Synthesis of dypnone using SO4/Al-MCM-41 mesoporous molecular sieves

The mesoporous molecular sieves Al-MCM-41 with Si/Al ratio equal to 16, was synthesized under hydrothermal conditions using cetyltrimethylammonium bromide (CTMA⁺Br⁻) as surfactant. The same ratio of Al-MCM-41 materials was impregnated using sulfuric acid, the materials as sulfated Al-MCM-41 (SO₄²⁻/Al-MCM-41). The mesoporous materials viz Al-MCM-41 and SO₄²⁻/Al-MCM-41 were characterized using several techniques e.g. ICP-AES, Nephelometer, XRD, FT-IR, TG/DTA, N₂-adsorption, solid-state-NMR, SEM and TPD-pyridine. ICP-AES studies indicated the presence of Al in the mesoporous materials. Nephelometer studies indicated the SO₄²⁻ presence of the SO₄²⁻/Al-MCM-41. XRD studies indicated that the calcined materials of Al-MCM-41 and SO₄²⁻/Al-MCM-41 had the standard MCM-41 structure. The surface area, pore diameter, pore volume and wall thickness of the mesoporous materials were calculated by BET and BJH equations, respectively. Crystallinity, surface area, pore diameter and pore volume of SO₄²⁻/Al-MCM-41 decreased except wall thickness and the expelling aluminum from the Al-MCM-41 framework increased the Lewis acidity. FT-IR studies indicated that Al-ions were incorporated in the hexagonal mesoporous structure of Al-MCM-41 and sulfuric acid was impregnated into hexagonal Al-MCM-41 materials. The thermal stability of as-synthesized Al-MCM-41 materials and SO₄²⁻/Al-MCM-41 materials were studied using TG/DTA. The environments of the Al-ions coordinated in the silica matrix were determined by ²⁷Al-MAS-NMR. The morphology of Al-MCM-41 and SO₄²⁻/Al-MCM-41 was determined by SEM. The total acidity of Al-MCM-41 and SO₄²⁻/Al-MCM-41 materials was determined by TPD-pyridine. The catalytic results were compared with those obtained by using sulfuric acid, amorphous silica–alumina, H-β, USY and H-ZSM-5 zeolites. The SO₄²⁻/Al-MCM-41 catalyst exclusively forms the product of dypnone from self-condensation of acetophenone molecules due to higher number of Lewis acid sites and has much higher yields than other catalysts except USY.     

Production of biodiesel by esterification of palmitic acid over mesoporous aluminosilicate Al-MCM-41

Biodiesel has been obtained by esterification of palmitic acid with methanol, ethanol and isopropanol in the presence of Al-MCM-41 mesoporous molecular sieves with Si/Al ratios of 8, 16 and 32. The catalytic acids were synthesized at room temperature and characterized by atomic absorption spectrometry (AAS), thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen absorption (BET/BJH), infrared spectroscopy (IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The reaction was carried out at 130 °C whilst stirring at 500 rpm, with an alcohol/acid molar ratio of 60 and 0.6 wt% catalyst for 2 h. The alcohol reactivity follows the order methanol > ethanol > isopropanol. The catalyst Al-MCM-41 with ratio Si/Al = 8 produced the largest conversion values for the alcohols studied. The data followed a rather satisfactory approximation to first-order kinetics.     

MCM-41介孔分子筛吸附性能的热力学和动力学分析

实验以亚甲基蓝作为模型吸附质,探讨了MCM-41介孔分子筛对模型吸附质亚甲基蓝的吸附性能,并对其吸附过程进行了热力学和动力学分析。结果表明,MCM-41介孔分子筛的吸附率高达94%,对亚甲基兰的吸附符合二级吸附动力学,MCM-41对亚甲基兰的吸附行为属于Freundlich等温吸附,整个吸附过程属于放热反应。     

分子筛催化合成正丁酸乙酯的研究

分子筛催化剂作为一种化工新材料在近年来得到了快速发展和广泛应用。正丁酸乙酯是一种重要的香料和用途较广泛的化工产品，本实验用硫酸特殊处理过的人造沸石作催化剂，合成了正丁酸乙酯。同时考察了合成条件对正丁酸和无水乙醇酯化反应的影响。适宜的条件为催化剂用量2g，n（正丁酸）：n（无水乙醇）=1：1，5，带水剂环己烷用量为10mL，反应温度为75℃～80℃，反应时间为3h。在此条件下正丁酸的转化率在80％以上。该催化剂可以重复使用。     

不同硅铝比Al-MCM-41介孔分子筛的表征及催化合成氯乙酸正辛酯

以十六烷基三甲基溴化铵( CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,乙二胺为碱性介质,当n(TEOS)∶n( NaAl02)∶n(CTAB)∶n(H2NCH2CH2NH2)∶n(H2O)=1∶x∶0.12∶ 3.5∶130,其中x=0.1,0.033,0.02,0.01,0.006 7时,水热法合成了Al - MCM - 41介孔分子筛.通过XRD,N2吸附-脱附,NH3 - TPD和TEM等手段对不同硅铝比(n(Si)/n(Al))的Al - MCM -41介孔分子筛进行了表征.结果表明,当n(Si)/n( Al)由150减小至30时,Al - MCM -41介孔分子筛仍具有典型的六方介孔结构特征,但当n( Si)/n(Al)=10时,样品结构有序性下降.Al - MCM - 41介孔分子筛酸量随着n( Si)/n( Al)减小而增大.将Al - MCM - 41介孔分子筛用于催化合成氯乙酸正辛酯,相同反应条件下,n( Si) /n( Al) =30的Al - MCM - 41介孔分子筛为催化剂时酯化率最高,由此表明,Al - MCM - 41介孔分子筛作为催化剂,反应酯化率不仅取决于样品酸量,也与其晶体结构相关.当Al - MCM - 41介孔分子筛用量为氯乙酸质量的3％,反应温度为120～140℃,n(氯乙酸)∶n(正辛醇)=1∶1.2时,酯化率可达94.34％.     

Immobilization of the heteropoly acid (HPA) H4SiW12O40 (SiW12) on mesoporous molecular sieves (HMS and MCM-41) and their catalytic behavior

Supported catalysts, consisting of SiW₁₂ immobilized on hexagonal mesoporous silica (HMS) and its aluminum-substituted derivative (MCM-41) with different loadings and calcination temperatures, have been prepared and characterized by X-ray diffraction, FT-IR and NH₃-temperature programmed desorption. It is shown that SiW₁₂ retains the Keggin structure on the mesoporous molecular sieves and no HPA crystal phase is developed, even at SiW₁₂ loadings as high as 50 wt%. In the esterification of acetic acid byn-butanol, supported catalysts exhibit a higher catalytic activity and stability and held some promise of practical application. In addition, experimental results indicate that the loaded amount of SiW₁₂ and the calcination temperatures have a significant influence on the catalytic activity, and the existence of aluminum has also an effect on the properties of supported catalysts.     

Influence of aluminium sources on the synthesis and catalytic activity of mesoporous AlMCM-41 molecular sieves

Mesoporous AlMCM-41 molecular sieves were synthesized using various aluminium sources, viz., sodium aluminate, aluminium sulphate, aluminium isopropoxide and pseudoboehmite. The influence of different aluminium sources on the framework substitution of aluminium as well as on the catalytic properties of t-butylation of phenol was studied. Among the aluminium sources, the use of sodium aluminate for the AlMCM-41 synthesis showed maximum incorporation of aluminium in the framework. Further, the catalyst also showed good catalytic activity for the chosen reaction.     

t-Butylation of p-cresol with t-butyl alcohol over mesoporous Al-MCM-41 molecular sieves

Selective liquid-phase t-butylation of p-cresol with t-butyl alcohol (t-BuOH) to produce 2-t-butyl-p-cresol (TBC) has been conducted over Al-MCM-41 catalysts with different Si/Al ratios. The effects of various reaction parameters such as temperature, reaction time and n_t-BuOH:n_p-cresol ratio on the conversion of p-cresol and the selectivity of TBC have been systematically investigated as well. When the Si/Al ratio of Al-MCM-41 catalysts is increased from 21 to 104 (respectively yielding Al-MCM-41(21), Al-MCM-41(42), Al-MCM-41(62), Al-MCM-41(83) and Al-MCM-41(104)), both the conversion of p-cresol and the yield and selectivity of TBC decrease due to the decrease of the number of Brønsted acid sites of the Al-MCM-41 catalysts. Al-MCM-41(21) catalyst is found to give the highest conversion of p-cresol (88.2%) and the highest selectivity of TBC (90.40%) under the optimal n_t-BuOH:n_p-cresol mole ratio of 2:1, the optimal reaction temperature of 90 °C and the optimal reaction time of 2 h. Furthermore, Al-MCM-41(21) can be recycled up to at least four times without losing its catalytic performance for butylation reaction.     

Small angle neutron scattering study of the structure and formation of MCM-41 mesoporous molecular sieves

The nanoscale structure and synthesis mechanisms of the MCM-41 class of inorganic mesoporous materials have been investigated by small angle neutron scattering (SANS). SANS measurements with solvents imbibed in the pores to vary the scattering contrast demonstrate that the low angle diffraction peaks from these materials are entirely due to the pore structure and that the pores are fully accessible to both aqueous and organic solvents. Static and shear flow SANS measurements on the concentrated cationic surfactant and silicate precursor solutions typically used in the synthesis of the mesopore materials indicate that the existence of preassembled supramolecular arrays that mimic the final pore structure is not essential for the synthesis of these materials.     

Redox behavior and selective oxidation properties of mesoporous titano- and zirconosilicate MCM-41 molecular sieves

Mesoporous titano- and zirconosilicate molecular sieves, Ti-MCM-41 and Zr-MCM-41, respectively, with Si/M ratios in the range from 11 to 96 (M=Ti or Zr), have been synthesized by the hydrothermal method and characterized by XRD, XRF, N₂ adsorption and diffusive reflectance UV–Vis (DRUV–Vis), FT-IR and electron spin resonance (ESR) spectroscopic techniques. The redox behavior and selective oxidation properties of these materials have been investigated. ESR of samples reduced with LiAlH₄ (298 K) and H₂ (673–873 K) reveals two types of metal ion species: species I^′ located inside the pore walls and species I^′′ located at the pore surface. The reduced species I^′′ are highly reactive towards oxygen and form M(O₂^−·) radicals. The M(O₂^−·) radicals were also observed when the samples were reacted with aqueous H₂O₂ or tert-butylhydroperoxide (TBHP). ESR studies reveal that Ti-MCM-41 is easier to reduce and reoxidize than Zr-MCM-41. The DRUV–Vis spectra are consistent with a monoatomic dispersion of the metal ions. In the samples with high metal loading the presence of a nanocrystalline metal oxide phase cannot be ruled out. Both Ti-MCM-41 and Zr-MCM-41 catalyze the hydroxylation of 1-naphthol with aqueous H₂O₂ and the epoxidation of norbornylene with TBHP.     

Ti incorporation in MCM-41 mesoporous molecular sieves using hydrothermal synthesis

Titanium-containing mesoporous materials (Ti-MCM-41) were obtained by hydrothermal synthesis. Such materials are active catalysts for the transesterification of dimethyl oxalate and phenol to produce diphenyl oxalate. To understand the role of the Ti in the catalytic process, Ti-MCM-41 samples with different Si/Ti ratios (from 5 to 100) were prepared and the samples were analyzed by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and ammonia temperature programmed desorption. It was concluded that the Ti is incorporated into the framework of the MCM-41 and formed weak Lewis acid sites. In addition, the number of Ti(IV) sites increased as the amount of titanium increased. X-ray powder diffraction, N₂ adsorption-desorption and transmission electron microscopy results showed that the Ti-MCM-41 samples have a hexagonal arrangement of mono-dimensional pores. A large number of Ti(IV) sites coupled with the mesoporous structure and large pore diameters are favorable for the transesterification catalytic properties of Ti-MCM-41.     

Reactions of turpentine using Zr-MCM-41 family mesoporous molecular sieves

The mesoporous molecular sieve Zr-MCM-41 was synthesized under hydrothermal conditions. Zr-MCM-41 material was impregnated using sulfuric acid to prepare SO ₄^2-/Zr-MCM-41. The obtained materials were characterized by XRD, FT-1R, N₂ adsorption/desorption and NH₃-TPD analysis technique. The results indicated that SO ₄^2-/Zr-MCM-41 was of better mesoporous structure, long range ordering and crystallites, and that SO ₄^2-existed in the skeleton of Zr-MCM-41 and enhanced its acidity. SO₄^2-/Zr-MCM-41 were firstly used as catalyst in the esterification of terpineol. The catalytic results were compared with those obtained by using sulfuric acid (33%), HY, HZSM-5 and SO₄^2-/ZrO₂ as catalysts. It was showed that SO₄^2-/Zr-MCM-41 were not only of better catalytic activity and selectivity, but also of better regenerable performance. The effects of synthesis methods of catalysts and Si/Zr mole ratio on catalytic properties were also studied. In addition, AlCl₃ was supported on the synthesized mesoporous molecular sieves to get composite catalysts that were firstly used to catalyze the polymerization of -pinene. It was showed that the catalytic result of the composite catalyst was better than that AlCl₃ alone.*To whom correspondence should be addressed. E-mail: yushitao@elong.com     

New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-41

New solid acid catalysts, consisting of heteropoly acid (HPA) H₃PW₁₂O₄₀ (PW) supported on a mesoporous pure-silica molecular sieve MCM-41, have been prepared and characterized by nitrogen physisorption, X-ray diffraction, FT-IR, and³¹P magic angle spinning NMR. The PW/MCM-41 compositions with PW loadings from 10 to 50 wt% have 30 Å uniformly-sized mesopores. HPA retains the Keggin structure on the MCM-41 surface and forms finely dispersed HPA species. No HPA crystal phase is developed even at HPA loadings as high as 50 wt%. PW/MCM-41 exhibits higher catalytic activity than H₂SO₄ or bulk PW in liquid-phase alkylation of 4-t-butylphenol (TBP) by isobutene and styrene. In the alkylation of TBP by styrene, PW/MCM-41 shows a size selectivity compared to bulk PW and PW/SiO₂, providing higher yields of a 2-(1-phenylethyl)-4-t-butylphenol, at the expense of the more bulky 2,6-bis-(1-phenylethyl)-4-t-butylphenol. The PW/MCM-41 compositions, having strong acid sites and a regular mesoporous system, are promising catalysts for the acid-type conversion and formation of organic compounds of large molecular size.     

Catalytic hydrodehalogenation of aryl halides, reduction of nitroarenes and reductive cleavage of azo compounds over mesoporous PdMCM-41 molecular sieves under transfer hydrogenation conditions

A novel, efficient and eco-friendly PdMCM-41 catalyst is put forward for the hydrodehalogenation of aryl halides, reduction of nitroarenes and reductive cleavage of azo compounds by catalytic transfer hydrogenation (CTH) method. The results indicate that the transformations occur in elegant and rapid manner with excellent yields. Furthermore, the catalyst can easily be recovered and reused without practically affecting the yields for up to three cycles.     

分子筛改性可降解材料聚乳酸的研究

将吸附有聚乳酸齐聚物的分子筛同工业级聚乳酸在双螺杆挤出机中造粒,制备了分子筛改性聚乳酸材料。研究了分子筛对聚乳酸力学性能的影响,添加量在7%~9%左右时可以起到最好的增强效果;复合材料可以在土壤中自然降解,增加分子筛添加量可以加快复合材料的降解。     

ZSM-5/MCM-41复合分子筛的微波合成及催化性能

用微孔沸石硅源法微波合成ZSM-5/MCM-41复合分子筛,采用XRD、BET和NH₃-TPD技术对合成分子筛进行表征。结果表明,复合分子筛具有类MCM-41 的典型六方介孔结构,同时具有中孔和微孔结构,复合分子筛的总酸量介于HMCM-41酸量与HZSM-5酸量之间。利用脉冲微反装置考察合成分子筛的邻二甲苯异构化催化性能。结果表明,ZSM-5/MCM-41复合分子筛具有高于同硅铝比的MCM-41、ZSM-5和ZSM-5/MCM-41的机械混合物的催化活性。     

Alkylation of phenol with methanol over AlPO and SAPO molecular sieves

This is the first preliminary report on alkylation of phenol with methanol over SAPO-5, SAPO-11 and SAPO-34 as well as over AlPO-5 molecular sieves at various temperatures. It has been established that on SAPO-5 only anisole, whereas on other molecular sieves cresols and anisole are simultaneously produced. On SAPO-34 and AlPO-5 formation of other cracking products were also observed. The selectivities generally determined by Broensted acidity of the molecular sieves, are also affected by other factors such as pore size and geometry. In the case of the AlPO-5 having initially high alkylation activity, a different mechanism is likely operative.     

硅源对全硅ＭＣＭ-４１中孔分子筛结构的影响研究

以十六烷基三甲基溴化铵、硅酸钠和正硅酸乙酯等为原料,研究了不同硅源对ＭＣＭ-４１分子筛合成的影响,并以ＸＲＤ、ＩＲ、热分析进行了表征,讨论了可能的机理。实验表明,用正硅酸乙酯比硅酸钠合成的全硅ＭＣＭ-４１分子筛的结构性能更好些。     

Me-OMS-1s分子筛催化叔丁基过氧化氢分解制备叔丁醇

采用静态水热法合成了Me-OMS-1s(Me=Mg,Co,Ni,Cu)分子筛催化剂,对合成的分子筛进行了X射线衍射和电感耦合等离子体发射光谱表征,并系统考察了反应温度(318~338 K)、反应时间(0.5~6 h)和催化剂用量(1.67~8.33 mg·ml^-1)对Me-OMS-1s催化叔丁基过氧化氢分解制备叔丁醇反应性能的影响。研究结果表明,合成的分子筛均为钡镁锰矿型(todorokite)氧化锰;在选择的多相催化反应条件下,Me-OMS-1s均有催化叔丁基过氧化氢歧化分解的反应活性,反应物叔丁基过氧化氢具有较高的转化率,产物叔丁醇的选择性均为100%。Me-OMS-1s催化叔丁基过氧化氢歧化分解的反应活性顺序为:Cu-OMS-1 > Mg-OMS-1 > Ni-OMS-1 > Co-OMS-1。叔丁基过氧化氢的转化率随反应温度的升高、反应时间的延长和Me-OMS-1s用量的增大而显著增大。