环己烷催化氧化制环己酮的MCM-41催化剂研究

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,采用水热合成法制备纯MCM-41分子筛和掺杂不同金属离子的MCM-41分子筛,并采用等体积浸渍法将一定量的金属离子负载在纯MCM-41分子筛内表面上,制备了负载型和掺杂型2类不同的MCM-41分子筛催化剂.分别考察了负载和掺杂的金属种类、金属Cr负载和掺杂量等对环己烷氧化制环己酮中的催化活性和选择性的影响.研究表明:采用掺杂制备的MCM-41分子筛催化剂活性明显高于负载型MCM-41分子筛催化剂;Cr掺杂量增加,虽然环己烷氧化转化率增加,但产物选择性下降;掺杂Cr的MCM-41分子筛催化剂,用于环己烷氧化制环己酮,在Si与Cr摩尔比为50以下、反应温度75℃、H2O2与环己烷摩尔比为1.2的条件下,环己烷的转化率可达60%左右,环己酮和环己醇的总选择性可达94%以上.     

WO3-ZSM-5/MCM-41催化剂的合成 及其催化氧化脱硫研究

以氢氧化钠溶液处理微孔沸石ZSM-5来提供硅铝源,合成了ZSM-5/MCM-41复合结构型分子筛。采用XRD、N2吸附脱附、TEM等方法对其进行了表征,考察了其水热稳定性。实验结果表明,碱处理合成的ZSM-5/MCM-41同时具有微孔孔道和介孔孔道结构,并具有优于介孔MCM-41分子筛的水热稳定性。以ZSM-5/MCM-41为载体负载三氧化钨后应用于噻吩/正辛烷模拟油体系,双氧水为氧化剂,催化氧化脱硫,WO3-ZSM-5/MCM-41（三氧化钨质量分数为10%）表现出良好的催化性能,脱硫率可达到93.6%。     

Synthesis,characterization and sulfide oxidation activity of vanadyl Schiff base complexes anchored on MCM-41

Vanadyl Schiff base complexes covalently attached on the surface of MCM-41 have been synthesized by anchoring Schiff base and subsequent reaction with VO(acac)₂. XRD, nitrogen adsorption and desorption, UV-visible spectroscopy and FT-IR show that vanadyl Schiff base complexes were successfully anchored on the surface of MCM-41 and the mesopore ordering decreased after the anchoring. The so-prepared heterogeneous catalysts have showed high activity for sulfide oxidation.     

In situ oxidation for stabilization of Fe/MCM-41 catalyst prepared by metal organic chemical vapor deposition

Oxygen has been found to be a key factor in the process of metal organic chemical vapour deposition (MOCVD) to stabilize the iron catalyst supported on MCM-41, particularly in the acidic aqueous reaction. Such stabilization is achieved by in situ oxidation of iron, which intercalates oxygen atoms into the framework of both siliceous and ferric oxides by developing Fe–O–Si and Fe–O–Fe bonds, respectively. This stable Fe/MCM-41 catalyst shows an excellent mineralization efficiency of orange II of ∼85% and an extremely low iron leaching concentration of ∼0.17 mg/L. The catalyst maintains its excellent catalytic activity after multiple reaction runs under acidic aqueous medium.     

High selective catalyst CuCl/MCM-41 for oxidative carbonylation of methanol to dimethyl carbonate

In this study, MCM-41 material was synthesised and the mesoporous structure was confirmed by powder XRD patterns. Organic group 3-chloropropyl was anchored on the surface of MCM-41(∞) by reaction of 3-chloropropyltrimethoxysilane with terminal silanol groups on the surface of MCM-41(∞) material. The modified material MCM-41(∞)-Cl still kept its mesoporous structure even after the material was calcined again at 550°C for 4 h and the organic groups were removed. Prepared by solid state ion-exchange under flowing nitrogen, CuCl/MCM-41 catalyst had 100% selectivity of dimethyl carbonate based on methanol and 5–10 wt.% conversion of methanol at 130°C. With the decreasing mole ratio of Si/Al of MCM-41 material, e.g. increasing the aluminium content in the material, the catalytic activity increased because more Cu^I was loaded on the material. When the reaction temperature increased, the dimethyl carbonate selectivity decreased and three by-products: dimethyl ether, methyl formate, dimethoxymethane were formed at high temperature. Finally increasing the oxygen partial pressure in the feed gases resulted in more dimethyl carbonate formed.     

MCM-41分子筛加氢裂化催化剂的研究

按水热法合成出介孔MCM-41分子筛，在不同的气氛下焙烧脱除有机模板剂。在固定床流动反应器上，与USY分子筛对比了正庚烷加氢裂化结果，发现MCM-41分子筛有较好的抗氮中毒能力，且其稳定时的加氢裂解活性比USY分子筛高。     

Characterisation and catalytic properties of MCM-41 and Pd/MCM-41 materials

Pure silica MCM-41 mesoporous molecular sieve material was synthesised and characterised by in situ synchrotron XRD, TEM, TGA/DTA and DRIFTS techniques. In situ energy dispersive XRD (EDXRD) confirmed the exact nature of the pore diameter of MCM-41 and the change in crystal structure on calcination. The IR band at 1057 cm^-1 of as-synthesised MCM-41 was shifted by 14 cm^-1 on heating to 673 K due to increased condensation of silanol groups to form Si-O-Si bridges. Calcined MCM-41 materials were used to support Pd, and the catalytic activities for 1-hexene and benzene selective hydrogenation were investigated. The Pd/MCM-41 catalyst showed high activity in hydrogenation of 1-hexene at an inlet reaction temperature of 298 K, but did not show any activity in hydrogenation for benzene. TEM results for the reduced Pd/MCM-41 catalysts revealed that the average Pd particle size was around 2-2.5 nm and these particles were located in the pores of MCM-41 and showed good distribution. TPR measurements showed that about 70% of palladium oxide (PdO) loading in the calcined catalysts was reduced at sub-ambient temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

MCM-48 supported chromium catalyst for trichloroethylene oxidation

MCM-48 supported chromium (Cr/MCM-48) catalyst was prepared by introduction of chromium chloride during gel-preparation for the hydrothermal synthesis of MCM-48. Based on the N₂ adsorption/desorption isotherm, BET, pore size distribution, XRD, FTIR, TGA, and DTA data, Cr/MCM-48 was found to have high surface area (832 m²/g), uniform pore size distribution (24 Å), mesoporous structures similar to MCM-48 itself, and incorporation of about 3 wt% of Cr component in the mesoporous framework. Cr/MCM-48 was very active for the oxidative destruction of trichloroethylene (TCE), which is a typical chlorinated volatile organic compound (CVOC); 100% conversion of TCE was achieved at 350°C. Based on the TGA of trichloroethylene/water adsorption study, it was found that MCM-48 had high adsorption capacity (>0.25 g TCE/g catalyst). In addition, the hydrophobicity of the adsorptive properties of Cr/MCM-48 materials could be modified. The high adsorption capacity and catalytic activity of Cr/MCM-48 material make it suitable for adsorption/catalysis bifunctional systems for energy-saving treatment of low concentration of VOC or CVOC.     

PW/MCM-41催化剂的合成及对合成柠檬酸三丁酯反应的研究

制备了负载H₃PW₁₂O₄₀(PW)杂多酸的PW/MCM-41催化剂,用XRD和BET等方法表征了催化剂的结构。在负载质量分数达40%的催化剂上,XRD未检测到PW杂多酸的晶相峰。考察了不同负载质量分数的 PW/MCM-41催化剂对反应的影响。重点讨论了催化剂的活化温度、酸醇摩尔比和反应温度等因素对酯化反应的影响。最佳操作条件：PW/MCM-41负载杂多酸催化剂的磷钨酸最佳负载质量分数 40%,催化剂焙烧温度300 ℃,酸醇摩尔比1∶4,反应温度140 ℃,反应时间6～7 h。实验结果表明,负载质量分数为40%的PW/MCM-41催化剂是替代硫酸合成柠檬酸三丁酯的理想催化剂,且稳定性良好。     

An efficient oxidation of cyclohexane over Au@TiO2/MCM-41 catalyst prepared by photocatalytic reduction method using molecular oxygen as oxidant

Cyclohexane oxidation using molecular oxygen as oxidant is one of the most challenge subjects. A novel photocatalytic reduction method to prepare Gold nanoparticles Au@TiO₂/MCM-41 was proposed. The prepared samples were characterized by XRD, N₂ adsorption isotherm, FT-IR, TEM and EDS. The results showed that gold nanoparticles were well-dispersed on TiO₂/MCM-41, and TiO₂ was dispersed on the surface of the support and the gold existed as Au⁰. Newly-developed catalyst was promising for the cyclohexane oxidation, achieving a turnover frequency (TOF) as high as 29,145 h^− 1 with 9.87% conversion of cyclohexane.     

A novel catalyst for clean production of diphenols—ferric trisacetylacetonate/MCM-41

Ferric trisacetylacetonate has been deposited within the zeolite MCM-41 and the product characterized by XRD and IR. In water at pH 7 it catalyzes the oxidation of phenol by H₂O₂, giving 58% conversion in 1 h at 50°C: products are catechol (66%), hydroquinone (27%) and benzoquinone (7%). Other oxidants and solvents are much less effective. UV-VIS spectra suggest a radical substitution mechanism, and a pollution-free process for phenol hydroxylation is now possible. ©1997 SCI     

Anchoring manganese acetylacetonate complex on MCM-41: Catalytic testing on limonene oxidation

This work reports the results of limonene oxidation in the liquid phase, over manganese acetylacetonate anchored onto MCM-41. Diluted t-butyl hydroperoxide is used as oxidant. Limonene oxide, carveol and carvone are formed, but the main product obtained is a polymer. The preservation of the MCM-41 channel system upon anchoring was checked by transmission electron microscopy (TEM), X-ray diffraction and nitrogen adsorption analysis. The complex anchoring was succeeded, since the catalyst could be used in four consecutive experiments. The maximum TOF values obtained for each run are similar and no significant metal complex leaching was observed (3% after the 4th run).     

Methanol oxidation on LaCo mixed oxide supported onto MCM-41 molecular sieve

Lanthanum cobaltate LaCoO_x supported onto MCM-41 mesoporous molecular sieve was prepared by in-situ oxidative decomposition of mixed LaCo citrate complexes inside the mesopores of this support. The prepared materials were characterized by EDX, EPR and UV-Vis DRS techniques as well as by N₂-BET measurements. The nanosized LaCoO_x particles within the mesopores of MCM-41 matrix contains cobalt atoms in lower than Co(III) average oxidation state. Also, the supported cobaltate does not form short-range order species of LaCoO₃ but presents as the highly disordered, oxygen deficient Co oxide nanophase. Catalytic activity in MeOH oxidation was tested using both conventional fixed-bed flow system and “operando” mode of DRIFT technique. The very high activity of MCM-41-supported cobaltate is not only due to highly dispersed LaCoO₃ phase but also because of rather low oxidation state of Co.     

Liquid-phase oxidation of cyclohexane using Co-P-MCM-41 catalyst

Co-P-MCM-41 catalyst was prepared by introduction of cobalt nitrate and phosphoric acid during gel-preparation for the synthesis of MCM-41. The catalyst, which was found to have very high surface area (995 m²/g), was tested for the one step liquid oxidation of cyclohexane to adipic acid using a semi-batch autoclave reactor (without addition of any promoter and solvent) at 115°C and in a flow of 5 bar of oxygen. The effect of the amount of catalyst on the induction time, catalytic conversion of cyclohexane, and selectivity to adipic acid was investigated. Depending on the amount of catalysts used in the reaction (from 0.1 to 3.0 g), an induction period from about 100 min to less than 10 min, cyclohexane conversion from 30 to 99%, and a selectivity to adipic acid from 15 to 40 %, could be achieved using Co-P-MCM-41 as the catalyst.     

MgO/MCM-41对二氧化碳的吸/脱附性能的研究

采用等体积浸渍法制备MgO/MCM-41作为吸附剂,通过静态吸附法对其吸附性能进行了测定。结果表明,制得的吸附剂只存在一个碱性位,二氧化碳吸附后主要以碳酸氢盐的形式存在。当MgO的负载量为20%的时候,对二氧化碳的吸附量最大,在30℃条件下,其对二氧化碳的吸附量为46.6 mg/g。     

PW/MCM-41光催化性能研究

以浸渍法制备了负载型光催化剂PW/MCM-41,并对催化剂进行了表征,考察了催化剂在光催化模拟染料废水亚甲基蓝(MB)溶液降解反应中的催化活性.实验结果表明:催化剂负载量为30％、催化剂投加质量浓度为3.0g/L、MB溶液的初始质量浓度为10 mg/L、pH=5、光照时间100 min时,对亚甲基蓝降解率可达91％以上...     

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.     

Pilot synthesis and commercial application in FCC catalyst of MCM-41 zeolite

MCM-41 zeolite in the grade of 600 kg was successfully synthesized and the MCM-41 added FCC catalyst was firstly prepared. The results indicate that the pilot samples of mesoporous Al-MCM-41 bear the typically uniform mesopore structure and considerable acidity and hydrothermal stability. The MCM-41 added FCC catalyst is positively capable to crack heavy oil feedstock, in which the yields of the diesel and lighter oil increased 1.85 and 3.47%, respectively and coke yield decreased 0.29%. Commercial application in FCCU indicate that optimization of nanopores of MCM-41 added faujasite zeolite might result in an industrial process to design novel FCC catalysts.     

Epoxidation of β-ionone using molecular oxygen over Pt/MCM-41 catalyst under mild conditions

The epoxidation of β-ionone over the Pt/MCM-41 catalyst using molecular oxygen in the liquid phase had been studied. The results indicated that the β-ionone was catalytically oxidized to 5,6-epoxy-β-ionone, 4-oxo-β-ionone, 4-hydroxy-β-ionone and dihydroactinidiolide using molecular oxygen as the sole oxidant. The effects of solvent, content of Pt, reaction temperature and time on the catalytic activity and product selectivity had also been investigated in detail.