介孔分子筛SBA-15的表面磺酸基改性及其催化性能

以正硅酸乙酯和3-巯丙基三甲氧基硅烷(MPTMS)为前驱体合成了不同丙磺酸含量的SBA-15-SO3H分子筛。通过X射线粉末衍射(XRD)、热失重、氮气等温吸附脱附、酸碱滴定、C.H.N.S元素分析和氨的程序升温脱附(NH3-TPD)等方法对样品进行了表征。结果表明,随着前驱体MPTMS含量的增加,SBA-15-SO3H样品的酸量和酸强度也随之增强。催化剂对水杨酸和碳酸二甲酯的酯化反应转化率和选择率可达98.09%和96.21%,催化活性随催化剂的酸量和酸强度的增强而增高。     

新型疏水性固体酸SBA-15-SO3H催化剂制备及其催化性能

采用水热法直接合成表面含丙磺酸基和不同烷基（如甲基、辛基和十六烷基）的疏水性介孔分子筛固体酸SBA-15-SO₃H。实验表明，固体酸的硫质量分数为3.53%～4.255%，酸含量为（0.84～1.08） mmol·g^-1，相对润湿接触角θ_{r(SBA-15-SO3H)}＜θ_{r(CH3-SBA-15-SO3H)}＜θ_{r(C8H17-SBA-15-SO3H)}＜θ_{r(C16H33-SBA-15-SO3H)}。催化剂对冰醋酸和正丁醇的酯化反应转化率可达75.5%，转化率随相对润湿角的增大而增大。     

有机-无机杂化介孔氧化硅凝胶材料的高效合成

同时采用正硅酸乙酯(tetraethylorthosilicate,TEOS)和甲基含氢硅烷[poly(methylhydrogen)siloxane,PMHS]作为反应组分[保持质量比m(TEOS)/m(PMHS)=6],通过溶胶-凝胶合成路线制备有机-无机杂化的介孔氧化硅凝胶材料。借助固体硅核磁共振、扫描电子显微镜、高分辨透射电子显微镜、低温氮气吸附/脱附、热分析和Fourier红外光谱等测试手段对杂化凝胶材料进行系统表征。分析结果表明:甲基化凝胶材料呈现"蠕虫状"孔道结构特征,孔径分布均匀,比表面积和孔体积分别为780m2/g和0.64cm3/g。     

介孔分子筛SBA-15-SO3H催化合成2-叔丁基对甲酚

以磺酸基介孔分子筛SBA-15-SO3H为催化剂,甲基叔丁基醚(MTBE)和对甲酚为原料合成了2-叔丁基对甲酚.考察了烷基化反应条件对反应转化率和选择性的影响以及催化剂的稳定性.结果表明,对甲酚转化率为87.4%,选择性为97.86%,SBA-15-SO3H分子筛是合成2-叔丁基对甲酚的理想催化剂.     

蒙脱土固体酸的制备及表征

利用鄂东膨润土为基质材料,制备了蒙脱土固体酸,并用XRD、TG DSC和FT IR对固体酸进行了表征。试验表明膨润土中蒙脱土含量越高、固体酸的催化效果越好。采用蒙脱土含量为84%的膨润土,经质量分数为10%的H2SO4和0.05mol·L-1Fe2(SO4)3处理得到的固体酸,比表面积从30m2·g-1增加到198m2·g-1,说明膨润土经过硫酸处理后,形成了大孔洞的骨架结构。该固体酸200℃活化后,催化萘与丙烯的烷基化反应,当用量为萘质量的15%、180℃反应6h,萘的转化率高达99.2%。     

水性硅溶胶-有机硅纳米杂化材料在陆水砂浆中的应用研究

将几种功能性有机硅烷偶联剂、含氢硅氧烷环状单体和含氢硅油与不同pH值的无机纳米硅溶胶水溶液反应制备出硅系有机-无机纳米杂化复合液和通过溶胶-凝胶法制出有机硅-硅溶胶杂化固体微粉,并用IR和TEM对杂化材料进行表征,研究了杂化复合液的稳定性和杂化复合液与杂化微粉中有机硅种类、杂化比和用量对水泥砂浆凝结硬化的影响和对聚合物改性水泥砂浆的强度和防水性能的影响.结果表明:(1)有机硅-硅溶胶杂化复合液对水泥砂浆有一定的缓凝作用;(2)改性砂浆的28d抗压强度都高于空白水泥砂浆的28d抗压强度.而且改性砂浆具有显著的防水功能;(3)杂化微粉改性水泥砂浆抗压强度接近于空白样,但吸水率较低,具有较佳的防水性能.     

WO3-TiO2-SO42-固体超强酸的制备及应用研究

TiO2·nH2O和H2WO4混合,其中w(H2WO4)=10%,然后用c(H2SO4)=1 mol/L的溶液浸渍,在600 ℃焙烧3 h,可制得Ho≤-14.52的WO3-TiO2-SO42-固体超强酸.其w(SO3)=4.7%,总酸量为0.85 mmol/g,比表面积为110 m2/g.用其催化乙酸丁酯液相酯化反应,乙酸转化率可达96%.     

无机杂化海藻酸钠渗透汽化膜的制备与分离性能对比

为提高海藻酸钠(SA)膜的渗透汽化分离性能,分别采用纳米氧化铝、纳米氧化锆和纳米氧化钛对SA膜进行改性,对比分析了3种不同杂化膜渗透汽化分离性能的差异,并将分离性能较好的杂化膜应用到乙酸与乙醇酯化反应脱水的体系中。系统考察了无机纳米粒子含量对SA膜渗透汽化分离性能的影响,对杂化膜进行了接触角、傅里叶红外(FTIR)、扫描电子显微镜(SEM)、热重/差示扫描量热(TG/DSC)、X射线衍射(XRD)和拉伸强度等表征与分析。结果表明,无机纳米粒子能提高SA膜的热稳定性、机械强度和渗透通量,当无机纳米粒子与SA质量比为0.3时,掺杂TiO_2、ZrO_2和Al_2O_3的杂化膜二碘甲烷的接触角依次升高,同时渗透通量也依次升高。SA-0.3Al_2O_3杂化膜亲水性较好,然而SA-0.3ZrO_2杂化膜分离性能最优,50℃下分离水含量10%的乙醇-水溶液,膜渗透通量达到336 g·m~(-2)·h~(-1),渗透侧水含量99.97%,分离因子29990。酯化反应脱水实验表明,在80℃时,酯化反应脱水实验乙酸转化率均高于无脱水实验乙酸转化率,平衡转化率不断被打破,反应12 h后,转化率由平衡时的79.3%提高到93.9%。     

WO3-TiO2-SO42-固体超强酸的制备及应用研究

TiO2.nH2O和H2WO4混合，其中w(H2WO4)=10%，然后用c(H2SO4)=1mol/L的溶液浸渍，在600℃焙烧3h可制得Ho≤-14．52的WO3－TiO2-SO4^2-固体超强酸。其w(SO3)=4.7%，总酸量为0．85mmol/g，比表面积为110m^2/g，用其催化乙酸丁酯液相酯化反应，乙酸转化率可达96％。     

二氧化硅-磺酸催化制备生物柴油的研究

通过溶胶-凝胶法制备二氧化硅,进而与氯磺酸反应制得二氧化硅-磺酸(SiO2-SO3H)固体酸催化剂,用于大豆油与乙醇的酯交换反应制备生物柴油,考察了催化剂的处理温度、乙醇与大豆油的摩尔比、催化剂用量、原料油油酸含量和反应时间的影响.结果表明,二氧化硅-磺酸(SiO2-SO3H)具有较高的酯交换反应催化活性.制备生物柴油的最佳条件如下:催化剂处理温度为120℃、醇油摩尔比为6∶1、催化剂质量分数为5.0%(以大豆油计)、正庚烷的质量分数(以大豆油计)为30.0%、反应时间为6.0 h,此时生物柴油产率可达97.84%.与固体碱催化剂相比,固体酸催化剂对原料的酸度有更强的适应性.     

Computational study on IM-5 zeolite: What is its preferential location of Al and proton siting?

The topological structure of IM-5 zeolite has remained a mystery for nearly 10 years. Stimulated by the recently structural solution of IM-5, we firstly report the computational study on the Al locations, acid sites and acid strength, which are important to understand the catalytic mechanism of IM-5. At the B3LYP/6-31+G(d,p) level, the 8T models were applied. The substitutions of Si by Al atom at 24 inequivalent tetrahedral crystallographic sites and the corresponding H proton localizations were examined by calculating the Al, H substitution energies, proton affinities, the atomic charges on proton and hydroxyl stretching vibrational frequencies. Based on the calculated results it was predicted that the most favorable sites for Al atom substitution in IM-5 were T4, T5, T14, T15 and T19 sites, whereas the least favorable sites were T1, T3, T8, T11, and T16 sites. There are about 40 preferable Al, H locations with relatively high acidity, including the nine strongest acid sites Al19H43 > Al14H18 > Al5H13 > Al4H8 > Al10H26, Al15H26, Al15H37, Al22H45 and Al24H47. The last five sites have equivalent proton affinity values. The numerous Al, H-sites with high acidity may be responsible for the high catalytic ability of IM-5. The calculated results should be helpful for understanding the chemistry of IM-5, the most complicated zeolite material known up to now.     

NU-87分子筛的合成与表征

考察了n(Na_2O)∶n(SiO_2)、n(H_2O)∶n(SiO_2)、n(SiO_2)∶n(Al_2O_3)及晶化时间对NU-87分子筛合成的影响,优化了合成条件,以EU-1分子筛为异质晶种,合成出NU-87分子筛,缩短了晶化时间。利用XRD、FT-IR、SEM及N_2等温吸附-脱附等方法对NU-87分子筛进行表征。结果表明,高n(H_2O)∶n(SiO_2)和低n(Na_2O)∶n(SiO_2)有助于NU-87分子筛的生成,优选的n(Na_2O)∶n(SiO_2)=0.14～0.15、n(H_2O)∶n(SiO_2)=48～55、n(SiO_2)∶n(Al_2O_3)=50、55和60时均合成出NU-87分子筛。晶化时间对NU-87分子筛的合成影响较大,最优晶化时间为8天。采用非晶种法合成NU-87分子筛时,随投料n(SiO_2)∶n(Al_2O_3)增大,合成NU-87分子筛的n(SiO_2)∶n(Al_2O_3)增大,比表面积逐渐减小,孔容与平均孔径大小基本未发生变化,B酸、L酸及总酸量逐渐减少。采用异质晶种法合成NU-87分子筛时,所得分子筛的n(SiO_2)∶n(Al_2O_3)最小,但其比表面积、孔容、平均孔径及B酸、L酸和总酸量均显著增大。NU-87分子筛为矩形条板状。     

Influence of initial Si/Al ratios on the structural,acidic and catalytic properties of nanosized-ZSM-5/SBA-15 analog composites prepared from ZSM-5 precursors

Nano-ZSM-5/SBA-15 analog composites (ZSC) were prepared in a two-step process from ZSM-5 precursors with different Si/Al molar ratios (10–50) via high-temperature synthesis in mildly acidic media (200 °C, pH 3.5) aiming to evaluate the influence of the initial Si/Al ratio on their structural, acidic and catalytic properties. The resulting materials were characterized by SAXS, XRD, FTIR, TEM, N₂ sorption, ²⁷Al solid state-NMR, NH₃-TPD, FTIR spectroscopy of adsorbed pyridine, AAS and ICP-AES. Under the applied synthesis conditions, a ZSC material with controlled distribution of nano-ZSM-5 and SBA-15 analog phases can be prepared from ZSM-5 precursors by adjusting the initial Si/Al ratio in the range of 20–30. Increasing the initial Si/Al ratio to 50, only ZSM-5 nanocrystals were obtained whereas reducing the initial Si/Al ratio to 10 led to the formation of a disordered mesoporous SBA-15 analog. The total acidity increases with the crystallinity of the ZSM-5 phase as varying the Si/Al ratio from 10 to 30 despite the decreased amount of incorporated aluminum. However, the acidity declines slightly when raising the Si/Al ratio to 50 because of the low incorporated aluminum. The catalytic performance of the ZSC materials compared to the reference materials, i.e. purely mesoporous Al-SBA-15 and purely microporous H-ZSM-5 was assessed in the gas phase cracking of cumene and 1,3,5-tri-isopropylbenzene (TIPB) as test reactions. The results show that a balanced ratio of nano-ZSM-5 and SBA-15 analog phases obtained by tuning the initial Si/Al ratio is crucial to achieve superior catalytic performance of the ZSC materials in the cracking of both cumene and TIPB.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Acid properties of mazzite zeolites studied by IR spectroscopy

The adsorption of ammonia, pyridine and benzene on non-dealuminated (Si/Al = 4.4) and dealuminated (Si/Al = 10 and 30) mazzite samples was followed by FT-IR spectroscopy. The dealumination of mazzites (by steaming and acid treatment) made all their narrow channels accessible to pyridine. Pyridine and ammonia adsorption and desorption showed that the broad OH band at approximately 3600 cm⁻¹ was composed of several submaxima corresponding to hydroxyl groups of various localizations and various acid strengths. With all the mazzite samples, the concentrations of Brönsted acid sites determined by ammonia adsorption were comparable with the values calculated from the chemical composition of zeolites (amounts of Al minus amount of Na) whereas those determined from pyridine adsorption were lower than these values. The greatest difference was found for the non-dealuminated MAZ-4.4, in which pyridine could not reach the sites of the narrow channels. The values of the extinction coefficients corresponding to the OH groups located in the large channels were higher than those corresponding to the OH groups of the narrow channels, thus showing the stronger acidity of the former OH groups. The acid strength of OH groups increased with the dealumination, as seen from the increase in the corresponding extinction coefficient and frequency shift Δν due to the hydrogen bonding of hydroxyl groups with benzene. Furthermore, the protonic acidity of the dealuminated mazzite of Si/Al = 30 was found to be stronger than that of mordenite and beta zeolite with comparable Si/Al.     

二甲醚水蒸气重整制氢CuO-ZnO-Al2O3-ZrO2/固体酸复合催化剂

Steam reforming(SR) of dimethyl ether(DME) was investigated for the production of hydrogen for fuel cells.The activity of a series of solid acids for DME hydrolysis was investigated.The solid acid catalysts were ZSM-5 [Si/Al=25,38 and 50:denoted Z(Si/Al)] and acidic alumina(γ-Al₂O₃) with an acid strength order that was Z(25)>Z(38)>Z(50)>γ-Al₂O₃.Stronger acidity gave higher DME hydrolysis conversion.Physical mixtures containing a CuO-ZnO-Al₂O₃-ZrO₂ catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR.DME SR activity strongly depended on the activity for DME hydrolysis.Z(25) was the best solid acid catalyst for DME SR and gave a DME conversion>90% [T=24℃,n(H₂O)/n(DME)=3.5,space velocity=1179 ml·(g cat)^-1·h^-1,and P=0.1MPa].The influences of the reaction temperature,space velocity and feed molar ratio were studied.Hydrogen production significantly depended on temperature and space velocity.A bifunctional catalyst of CuO-ZnO-Al₂O₃-ZrO₂ catalyst and ZSM-5 gave a high H₂ production rate and CO₂ selectivity.     

十氢萘在HY和Beta分子筛上加氢开环的研究

采用高温高压反应釜研究了十氢萘在低硅铝比HY分子筛[n(Si)/n(Al)=3.2]、Beta分子筛n(Si)/n(Al)=9.7]和双功能催化剂Pt-HY、Pt-Beta上的加氢开环反应,考察了分子筛孔道结构及酸性质、贵金属Pt及反应温度等因素对十氢萘转化率和产物选择性的影响。结果表明,十氢萘在Beta分子筛上的转化率较高,且有大量脱氢缩合产物（DHC）生成。Pt引入HY和Beta分子筛后,初始反应速率升高,十氢萘转化率增加,C₁₀产物中开环异构比增大,Beta分子筛上的脱氢缩合反应得到抑制。反应温度升高可以提高十氢萘在HY分子筛上的转化率,使得C₁₀产物选择性下降,而开环异构比（ROP/Iso）增大。     

催化剂结构与焦油模型化合物裂解行为的关联性

以Ni（NO₃）₂·6H₂O为镍源,分别以HZSM-5（Si/Al=25）、HZSM-5（Si/Al=50）、HZSM-5（Si/Al=200）、USY、Al₂O₃为载体制备了5种镍基催化剂,采用XRD、H₂-TPR、BET、NH₃-TPD等方法对其进行了表征,在固定床反应器中考察了上述催化剂对煤焦油模型化合物甲苯+芘的催化裂解性能。结果表明,相比惰性载体石英砂,在催化剂作用下,液相产物中轻质芳烃种类明显增多。3种Ni/HZSM-5催化剂的比表面积和平均孔径较为接近,然而酸性中心数量最多的Ni/HZSM-5（Si/Al=25）,对甲苯+芘的裂解能力最强,体现为液体产物收率最低（仅为15.95%）,气产率和析碳率均最高,分别达16.73%和67.32%。在酸性中心数量相近的Ni/HZSM-5（Si/Al=200）与Ni/Al₂O₃作用下,液体产物收率差别较小,但后者的芘裂解率比前者高41.47%,主要是由于后者的平均孔径比前者高1.64倍,说明平均孔径大有利于重质组分芘的裂解。综合考虑液体产物收率、气产率、析碳率和芘的裂解率,Ni/Al₂O₃更适合甲苯+芘裂解反应体系。     

粒径对磺酸官能化介孔材料性能的影响

以聚乙氧基-聚丙氧基-聚乙氧基三嵌段共聚物(P123)为模板剂、正硅酸乙酯(TEOS)为硅源,保持P123和TEOS的浓度比,改变P123和TEOS在合成体系中的浓度,水热法合成了系列具有不同粒径的介孔分子筛SBA-15.采用后合成法,将3-巯基丙摹三甲氧基硅烷(MPTMS)嫁接到具有不同粒径的介孔分子筛SBA-15表面上,经氧化后得到含有强酸性的磺酸基因的固体酸样品SBA-15-SO_3H.采用SEM、XRD、FT-IR、TG-DTA、N_2吸附以及酯化反应考察了粒径对所制备的SBA-15-SO_3H的物化性能和催化性能的影响.结果表明,SBA-15的粒径大小对MPTMS在其上的嫁接量没有很人影响,但对后续氧化过程有较大的影响,SBA-15粒径的减小有利于巯基被氧化为磺酸基,导致磺酸的负载量随着粒径的减少而增大.SBA-15-SO_3H在乙酸和乙醇的酯化反应中表现出不同的催化性能,催化性能的差异是粒径大小、酸量及磺酸基和巯基相互作用的综合结果.