Preparation of High-Density Fuel Through Dimerization of β-Pinene

High-density fuel was prepared by catalytic dimerization and subsequent hydrogenation. Different amounts of phosphotungstic acid (H₃PW₁₂O₄₀, HPW) were loaded on mesoporous silica (SBA-15) by a simple impregnation method to prepare HPW/SBA-15 catalysts. The prepared catalysts were mesoporous. Characterizations indicated that the dispersion and the specific surface area depend on the HPW amount. The obtained dimers from catalytic dimerization of β-pinene underwent isomerization and then dimerized to form the heterogeneous products. At the optimum load of HPW, the HPW/SBA-15 catalyst displayed the highest catalytic activity and the increased yield of dimer for a 3-h reaction. After the subsequent hydrogenation reaction, the obtained hydrogenated dimer products displayed a density and a volume calorific value comparable to those of commercial JP-10.     

SBA-15负载杂多化合物在苹果酯合成中的催化性能

用浸渍法制备了一系列中孔二氧化硅分子筛SBA-15负载的磷钨酸(PW)及其铯盐和钾盐催化剂,考察了其在乙酰乙酸乙酯与乙二醇缩合制苹果酯反应中的催化性能, 并以N2吸附,Hammett指示剂和FT-IR等手段表征了催化剂的物化性质, 在水处理试验中考察了催化剂的稳定性,溶脱到水中的杂多化合物浓度用紫外可见分光光度仪测定.结果表明,在合成苹果酯的反应中,当PW的负载量低于30%,杂多酸盐负载量低于20%时,固体催化剂无活性;催化剂在反复使用过程中活性下降的量与活性组分在极性体系中的溶脱量成对应关系,说明催化剂活性下降的主要原因是杂多酸(盐)活性组分的流失造成的,而负载磷钨酸铯盐良好的催化稳定性来源于磷钨酸铯盐的难溶脱性.     

负载杂多酸(盐)的表征及其在苹果酯合成反应中的催化性能

用浸渍法制备了一系列负载型磷钨酸及其铯盐催化剂,载体包括超稳Y沸石（USY）、脱铝超稳Y沸石（DUSY）、SiO₂和SBA-15,测定了催化剂的比表面积和酸强度,并在乙酰乙酸乙酯与乙二醇液相缩合制取苹果酯反应中考察了催化剂的性能.结果表明,这些负载型杂多化合物催化剂都表现出较高的催化活性.然而,催化剂在水中的溶脱性能实验表明,负载型磷钨酸催化剂存在严重的活性组分流失现象,不能重复使用,而DUSY负载的磷钨酸铯盐催化剂不仅表现出较高的催化活性,而且显示出较好的重复使用性能.在优化的反应条件下30% (质量分数) Cs_2.5H_0.5PW/DUSY催化剂上乙酰乙酸乙酯的转化率可达98.7%,苹果酯的选择性大于97%.     

A Comparative Study of the Conversion of 2-Methylpent-2-ene on 12-Tungstophosphoric, 12-Tungstosilicic and 12-Molybdophosphoric Acids: An Acidity Probe

The conversion of 2-methylpent-2-ene (2M2PE) is employed as a probe reaction to investigate the acidic properties of 12-tungstophosphoric acid for various loadings on silica, residence times, time-on-stream and reaction temperatures. The high selectivities to methyl shift products as compared with those to double-bond shifts indicate the presence of strong acid sites. Infrared spectra show that adsorbed 2M2PE exists as saturated species on the surface of HPW/SiO₂ with irreversibly adsorbed material forming conventional coke. Similar conversions of 2M2PE and selectivities to products are obtained with 12-tungstosilicic acid supported on SiO₂ while with 12-molybdophosphoric acid the conversions are markedly lower and the highest selectivities are found with products obtained from double-bond shifts, indicating the presence of relatively weak acidic sites. The results obtained from 2M2PE conversion on other acidic catalysts are compared with those from the supported heteropoly acids.     

磷钨酸/SBA-15催化氧化-萃取柴油脱硫

以自制的SBA-15为载体,磷钨酸为活性组分,用过量浸渍法制备了HPW/SBA-15催化剂,并采用SEM、BET和TG-DTA对催化剂进行表征分析。H₂O₂为氧化剂,十六烷基三甲基溴化铵（CTAB）为相转移剂,以二苯并噻吩（DBT）的模型化合物（DBT为溶质、正辛烷为溶剂）进行氧化脱除为探针反应,考察了磷钨酸负载量和HPW/SBA-15的焙烧温度对催化剂活性的影响,同时考察了氧化-萃取工艺条件对真实柴油脱硫效果的影响。实验结果表明,磷钨酸最佳负载量为30%,HPW/SBA-15在250℃焙烧处理时活性最高;在n(H₂O₂)：n(S)=6、HPW/SBA-15用量为2.5%（基于柴油质量）、CTAB用量为0.4%（基于柴油质量）、萃取级数为4、温度60℃反应1.5h的条件下,柴油硫含量从1317mg/L降到39mg/L,脱硫率达到97.0%、收率不低于85.0%。气相色谱结果显示,该催化氧化脱硫体系容易脱除柴油中加氢难以脱除的二苯并噻吩及其衍生物。     

Activity and stability of amino-functionalized SBA-15 immobilized 12-tungstophosphoric acid in the oxidative desulfurization of a diesel fuel model with H2O2

In this study, the stability and the catalytic activity of an ordered mesoporous SBA-15 immobilized 12-tungstophosphoric acid (H₃PW₁₂O₄₀, HPW) in the oxidative desulfurization (ODS) of benzothiophene (BT) and dibenzothiophene (DBT) were improved by a post-synthesis-grafting method. In this method, SBA-15 was functionalized to provide a large number of amine groups for the immobilization of HPW through electrostatic binding with (3-aminopropyl) triethoxysilane (APTES) using triflic acid as a protonated agent. The materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N₂ adsorption–desorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results show that the structure of functionalized SBA-15 support and the active phase of the HPW remained intact after immobilization. The synthesized PW^–H₃N⁺-SBA-15 catalyst showed a high catalytic activity for ODS, achieving BT and DBT conversion of 99.9% and 100% with the reaction conditions of reaction temperature of 50?°C, H₂O₂ dosage of 1?mL, catalyst dosage of 0.03?g, and reaction time 5 and 1?h, respectively. The catalyst also showed a high reusability after up to four cycles, for which the conversion of the fourth reaction was 90.0% for both BT and DBT.     

SiW12／SBA-15介孔分子筛催化合成月桂酸乙酯

用传统的水热合成法制备纯硅介孔分子筛SBA-15,将SiW12负载在SBA—15上。采用x射线衍射（XRD）、红外光谱（IR）对不同负载量的催化剂进行了表征。表征结果表明,催化剂SiW12／SBA-15仍具有纯硅SBA-15的介孔结构,SiW12的Keggin结构保持完整。该催化剂用于月桂酸与乙醇的酯化反应,重点考察了硅钨酸的负载量、反应温度、酸醇比、催化剂用量等因素对酯化反应性能的影响。得到最佳反应条件为：硅钨酸的负载量为25％,反应温度90℃,酸醇比1：2．5,催化剂用量为月桂酸质量的1％,反应时间4h。催化剂再生实验结果认为,SiW12／SBA-15介孔分子筛具有良好的再生性能和稳定性。     

Application of Cs salt of 12-tungstophosphoric acid supported on SBA-15 mesoporous silica in NO x storage

Cs salt of 12-tungstophosphoric acid (HPW) was deposited simultaneously at the external surface of the SBA-15 silica microcrystals and inside its mesoporous channels at loading of 60 wt% and Cs/W ratio in the range between 0.9 and 2, followed by impregnation of 1 wt% Pt. The performance of the Pt/CsHPW/SBA-15 composite materials was tested in the NO _x storage. The optimal NO _x storage capacity and efficiency were achieved at Cs/W of 1.5. The dispersion of CsHPW on SBA-15 led to a significant decrease of its crystal size (5–13 nm) compared with bulk HPW and HPW supported on titania (28–29 nm). Pt/CsHPW/SBA-15 displayed lower NO _x absorption capacity but much higher absorption and desorption efficiency than the reference Pt/HPW and Pt/HPW/TiO₂ materials. Consequently, Pt/CsHPW/SBA-15 displayed a better performance in short lean (2 min)—rich (1 min) absorption-desorption cycles. The novel Pt/CsHPW/SBA-15 nanocomposites presents the basis for improved storage material for NO _x removal from lean exhaust gases in highly dynamic aftertreatment technologies.     

MgO-SBA-15 Supported Pd-Pb Catalysts for Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate☆

Novel MgO–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein (MAL) with methanol to methyl methacrylate (MMA). The MgO–SBA-15 supports were synthesized with different...     

固体酸催化合成乳酸丁酯

锡、镁、铁、铜和镍等不同金属掺杂的磷酸铝固体酸、杂多磷钨酸及其二氧化硅负载的催化剂用于乳酸正丁酯的合成,考察了各种反应条件的影响。结果表明,反应温度是重要的影响因素,反应温度以120 ℃较适宜。二氧化硅负载的杂多磷钨酸催化剂是较好的催化剂,而且负载的HPW/SiO₂催化剂能大大减少杂多磷钨酸的用量。     

Oxidative desulfurization of diesel fuel by mesoporous phosphotungstic acid/SiO2: the effect of preparation methods on catalytic performance

Two kinds of mesoporous phosphotungstic acid/SiO₂ (HPW/SiO₂) have been synthesized by amino-functionalized (AF) method and evaporation-induced self-assembly (EISA) method, and their catalytic performance was investigated for deep oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in diesel oil. Various analysis techniques such as XRD, TEM, N₂ adsorption/desorption isotherms, FT-IR and ³¹P MAS NMR spectra have been used to investigate the pore structure and chemical properties of the resultant catalysts. The structural and spectroscopic analysis indicates both catalysts have a highly ordered 2D hexagonal mesostructure. HPW/SiO₂-EISA can maintain the Keggin structure of HPW molecules and has a high BET surface area (403 m²/g). But in the AF method, the mesostructure of SBA-15 are partially blocked after the introduction of HPW molecules, and the Keggin structure of HPW molecules has been damaged. The catalytic performance results also show that HPW/SiO₂-EISA exhibits higher catalytic activity and stability compared to HPW/SiO₂-AF. As for HPW/SiO₂-EISA, the conversions of DBT, 4,6-DMDBT and BT are found to be 99.6, 97.6, 94.8 %, respectively. It shows a good maintenance of activity even after the 7th cycle of use. While corresponding conversions by using HPW/SiO₂-AF are found to be 90.2, 89.1 and 87.6 %, and the DBT conversion decreases to 75.7 % after the 5th cycle of use.     

Synthesis and characterization of W-SBA-15 and W-HMS as supports for HDS

W-modified HMS and SBA-15 mesoporous materials (Si/W molar ratio equal to 40) were synthesized using sodium tungstate as tungsten source. In order to prepare NiW catalysts these mesoporous materials were impregnated with an aqueous solution of nickel salt of 12-tungstophosphoric acid Ni_3/2PW₁₂O₄₀. The synthesized W-HMS, W-SBA-15 materials and NiW catalysts have been characterized by S_BET, XRD, UV–Vis DRS, FT-IR, TPD of NH₃, ²⁹Si MAS NMR, SEM and HRTEM. The influence of these particular supports on catalytic activity of NiW catalysts was studied in the reaction of hydrodesulfurization (HDS) of thiophene. The results from the FT-IR and UV–Vis DR spectroscopy confirm incorporation of W into the HMS and SBA-15 structures. Additionally ²⁹Si MAS NMR measurements revealed relatively stronger effect of W ion incorporation in HMS structure on degree of silica cross-linking as compared to the effect of W ion incorporation in SBA-15 structure. The catalytic study showed that both W-HMS and W-SBA-15 materials modified with W are good supports for NiW catalysts in the HDS reaction of thiophene. The catalysts show lower selectivity for butanes than a reference NiW/γ-Al₂O₃ catalyst leveling of about 10% for chosen experimental conditions.     

固体超强酸SO42-/ZrO2/SBA-15的合成及其催化活性

水热合成了介孔材料SBA-15,并以其为载体负载固体超强酸SO42-/ZrO2,通过XRD和N2吸附/脱附对制备的SO42-/ZrO2/SBA-15催化剂进行了表征。在固定床反应器中,以丙烯和乙酸为原料,研究了该催化剂合成乙酸异丙酯的活性。结果表明实验制备的催化剂具有较好的介孔结构,并在乙酸异丙酯的合成中表现出了良好的活性。     

SiW_(12)/SBA-15介孔分子筛催化合成月桂酸乙酯

用传统的水热合成法制备纯硅介孔分子筛SBA-15,将SiW12负载在SBA-15上.采用X射线衍射(XRD)、红外光谱(IR)对不同负载量的催化剂进行了表征.表征结果表明,催化剂SiW12/SBA-15仍具有纯硅SBA-15的介孔结构,SiW12的Keggin结构保持完整.该催化剂用于月桂酸与乙醇的酯化反应,重点考察了硅钨酸的负载量、反应温度、酸醇比、催化剂用量等因素对酯化反应性能的影响.得到最佳反应条件为:硅钨酸的负载量为25%,反应温度90 ℃,酸醇比1:2.5,催化剂用量为月桂酸质量的1%,反应时间4 h.催化剂再生实验结果认为,SiW12/SBA-15介孔分子筛具有良好的再生性能和稳定性.     

Novel route to control the size,distribution and location of Ni nanoparticles in mesoporous silica for steam reforming of propylene glycol in microchannel reactor

Highly dispersed and size controlled Ni nanoparticles (NPs) in SBA-15 were synthesized by thermolysis of sucrose as a new delivery conveyor and sacrificial template. The Ni/SBA-15 catalysts were characterized systematically to elucidate their morphological structure and surface properties. It was found that the sucrose contributes majorly to control the size and higher distribution of Ni NPs by prevents their sintering into mesoporous nanochannels. The catalytic performance of Ni/SBA-15 catalysts was investigated by steam reforming of propylene glycol in microchannel reactor. As compared with conventional Ni-impregnated catalyst, the catalyst prepared with sucrose assisted route improves the coking and sintering resistance in steam reforming reaction of propylene glycol.     

介孔分子筛SBA-15的改性研究进展

从金属改性、酸改性和氧化物改性三方面综述了介孔分子筛SBA-15的改性研究进展,重点介绍了SBA-15表面功能化后引入金属改性的方法。评述了金属纳米粒子的制备对改性的SBA-15催化剂催化性能的影响。     

Preparation of Keggin and Preyssler Heteropolyacid Catalysts on Amine-modified SBA-15 and Their Catalytic Performances in Esterification of n-Butanol with Acetic Acid

The Keggin and Preyssler-structured tungstophosphoric acid catalysts anchored on the surface of modified SBA-15 (KNS and PNS) by grafting amine groups into system, and were characterized by infra-red spectroscopy, X-ray diffraction, N₂-adsorption, Hammett indicator and UV-Vis spectroscopy. Their catalytic behaviors were investigated in the esterification of n-butanol with acetic acid. Characterization results for obtained catalysts verified the ordered hexagonal mesostructure of SBA-15 and preservation of the structures of heteropolyanions on amine-modified SBA-15. KNS and PNS catalysts with the 37 and 25% loadings of Keggin and Preyssler acids exhibited considerable conversions of n-butanol of 61.2 and 63.8% with both 100% selectivity for n-butyl acetate in the esterification reaction, respectively. Especially, tests of six-cycle reaction revealed good reusabilities of KNS and PNS due to their excellent water-resistance properties, and in contrast, the catalysts prepared by direct impregnation lost their high activities immediately at their second cycles. Active sites on the amine-modified SBA-15 retained the Keggin or Preyssler structure after reaction demonstrated by IR analysis. Also, reaction conditions such as the amount of catalyst, reaction time and temperature were explored.     

M/SBA-15(M=Cu、Fe、Cr)介孔分子筛的制备、表征及其催化NO+CO反应研究

以介孔分子筛SBA-15为载体,采用浸渍法制备M/SBA-15(M=Cu、Fe、Cr) 介孔分子筛催化剂。采用XRD、BET、FT-IR、H₂-TPR和XPS等对样品进行分析表征,在固定床微型反应器中评价M/SBA-15(M=Cu、Fe、Cr)分子筛催化剂催化NO+CO的反应性能。结果表明,负载金属的SBA-15分子筛仍保持高度有序的二维六方介孔结构,比表面积和孔径略有减少,负载的活性金属组分在SBA-15分子筛表面具有较高的分散度。Cu/SBA-15、Cr/SBA-15和Fe/SBA-15催化剂对NO+CO反应体系均有一定活性,但由于活性金属自身的特性及其在载体表面负载量的差异,3种催化剂上呈现的NO还原活性不同,顺序为：Cr/SBA-15＞Cu/SBA-15＞Fe/SBA-15。     

A mesoporous Pt-SBA-15 nano architecture with catalytic functions on oxidation of CO

Among many kinds of noble metal catalysts, platinum is the most efficient and widely used as automotive exhaust catalysts for treatment to remove poison gases. Due to the regular pore system and controllable pore size, mesoporous silica has been acknowledged as supports of adsorption, separation, catalysts for the extremely large surface areas and shape selective properties. SBA-15 supported Pt particles are prepared by a facile method and characterized by X-ray diffraction, Transmission Electron Microscopy and N₂ isotherms techniques. Results indicate that the Pt precursor is introduced into the mesoporous successfully and all of the particles are confined in SBA-15 with monodispersed form and uniform size. The catalytic activity of Pt-SBA-15 on oxidation of carbon monoxide are also investigated and the result indicate that the catalysts possess high catalytic activity, catalytic efficiency and stability on oxidation of CO.     

Preparation of Mesoporous Catalyst Supported on Silica with Finely Dispersed Ni Particles

A novel nickel catalyst supported on SBA-15 type mesoporous silica was synthesized by the grafting of N-(trimethoxysilylpropyl)ethylene diamine triacetic acid salt (EDTA) onto the surface of SBA-15 and followed by adsorption of nickel ions and calcinations (Ni-E-SBA). The catalysts prepared were characterized using XRD, TEM, TED, SAXS and N₂ adsorption/desorption measurements. While nickel particles loaded on catalysts prepared by the wet impregnation method were found to be aggregated on the outer wall of the supports, nickel particles were finely dispersed on the surface of the mesopores in the Ni-E-SBA catalyst. The catalytic performances of the prepared catalysts were evaluated using the hydrodechlorination (HDC) of 1,1,2-trichloroethane (TCEa) as a model reaction. Results showed that the Ni-E-SBA catalyst had the highest activities of the catalysts examined under the given conditions.