ZSM-5/SBA-15催化氧化脱硫催化剂的制备表征及脱硫性能研究

结合分子筛ZSM-5与SBA-15自身的优点,合成了不同质量比例的ZSM-5/SBA-15微孔-介孔复合分子筛,并进行XRD、N2吸附-脱附表征,分析其结构特征。以其为载体负载金属W、Ni、Ce、Cu,制备出不同的氧化脱硫催化剂,对模拟油进行氧化脱硫研究。结果表明,负载金属W制备出的WO3-ZSM-5/SBA-15(ZSM-5质量分数为10%)复合分子筛,脱硫效果最好,脱硫率为75.44%。     

ZSM-5/SBA-15催化氧化脱硫催化剂的制备表征及脱硫性能研究

结合分子筛ZSM-5与SBA-15自身的优点,合成了不同质量比例的ZSM-5/SBA-15微孔-介孔复合分子筛,并进行XRD、N2吸附-脱附表征,分析其结构特征。以其为载体负载金属W、Ni、Ce、Cu,制备出不同的氧化脱硫催化剂,对模拟油进行氧化脱硫研究。结果表明,负载金属W制备出的WO3-ZSM-5/SBA-15(ZSM-5质量分数为10%)复合分子筛,脱硫效果最好,脱硫率为75.44%。     

Oxidation-extraction desulfurization of model oil over Zr-ZSM-5/SBA-15 and kinetic study

ZSM-5/SBA-15 composite molecular sieves were synthesized using post-synthesis method and characterized by X-ray diffraction and N₂ adsorption-desorption. The oxidative-extration desulfurization of model oil was investigated by using hydrogen peroxide as the oxidant, tetrabutyl ammonium bromide as phase transfer catalyst, dimethyl sulfoxide as extractant, and Zr-ZSM-5/SBA-15, Ag-ZSM-5/SBA-15, Ce-ZSM-5/SBA-15 as catalyst. Under the optimal conditions, the desulfurization rate decreases in the order: Zr-ZSM-5/SBA-15>Ce-ZSM-5/SBA-15 > Ag-ZSM-5/SBA-15. The highest desulfurization rate is 84.53% under the catalysis of Zr-ZSM-5/SBA-15. Kinetics analysis shows that the reaction is pseudo-first-order with the activation energy of 44.23 kJ/mol.     

Zn/SBA-15介孔吸附剂的制备及脱附低浓度H_2S性能

以介孔材料SBA-15为载体、过渡金属（Zn、Fe、Mn、Cu、Co和Ni）氧化物为活性组分,用等体积浸渍法制备了过渡金属氧化物负载型介孔脱硫剂,通过XRD和比表面积测定对其进行表征。结果显示,Zn负载的SBA-15对H2S吸附效果最好;Zn离子负载量为23%时,Zn/SBA-15对H2S穿透吸附量最大,为29.7 mg/g吸附剂;考察流速、反应温度以及杂质气体存在对Zn/SBA-15吸附脱除低浓度H2S的影响,并研究了Zn/SBA-15吸附脱除H2S的再生性能,结果表明在空气氛围下,Zn/SBA-15吸附剂在573 K可再生,循环使用4次穿透硫容不发生变化。     

离子交换温度对Ag基介孔材料吸附剂脱硫性能的影响

采用离子交换法将Ag+交换到铝化的SBA-15上,通过改变交换温度得到Ag含量分别为1.05,1.32,1.46和1.47(wt)%的Ag/Al-SBA-15吸附剂。N2吸附结果表明,所制备的吸附剂保持了介孔材料的结构。常温、常压下,对商业柴油(含硫量为0.0191(wt)%)的吸附脱硫表明,改性后吸附剂的硫容量提高了37.2%。再生实验表明,吸附剂的脱硫性能可100%恢复。     

Co掺杂对Ce/MCM-41和Ce/SBA-15催化剂催化氧化甲苯性能的影响

以分子筛为载体,采用等体积浸渍法制备Ce/SBA-15、Ce/MCM-41、Ce Co/SBA-15和Ce Co/MCM-41催化剂。用N2吸附-脱附、X射线衍射、扫描电子显微镜、H2程序升温还原、X射线光电子能谱和傅立叶变换红外光谱等对载体和催化剂进行表征,并考察催化剂催化氧化甲苯的活性。结果表明,与载体相比,随着Ce和Co的浸渍,催化剂的比表面积和孔容下降,但仍然保持了载体的有序介孔结构。引入的Ce和Co没有进入分子筛骨架,而是以立方相固溶体形式存在于分子筛表面和孔道中。催化剂催化氧化甲苯活性顺序依次为:Ce Co/SBA-15>Ce Co/MCM-41>Ce/MCM-41>Ce/SBA-15。共浸渍Ce和Co的催化剂活性明显优于只浸渍Ce的催化剂,活性与其还原性能直接相关,Ce Co/SBA-15催化剂具有最低的还原温度和最好的供氧能力,从而表现出最优的催化性能。     

Investigation of CuO/mesoporous SBA-15 sorbents for hot gas desulfurization

Metal oxides, are widely used as sorbents to remove H₂S from hot gases produced by gasification processes. These oxides, however, suffer from several problems such as low capacity, sintering, evaporation, low duration and mechanical strength. Pure metal oxides or their admixtures loaded on inert materials have been used to overcome these problems.     

Enhanced desulfurization performance of hybrid membranes using embedded hierarchical porous SBA-15

The utilization of materials with a hierarchical porous structure as multi-functional additives is highly attractive in the preparation of hybrid membranes. In this study, novel hybrid membranes are designed by embedding hierarchical porous Santa Barbara Amorphous 15 (SBA-15) with a dual-pore architecture (micropores and mesopores) for pervaporation desulfurization. The SBA-15 with cylindrical mesopores provides molecular transport expressways to ensure improved permeability, while micropores on the wall have molecular sieving effects that are essential for the enhancement of permselectivity of thiophene molecules. Considering thiophene/n-octane mixture as a model system, the hybrid membrane with embedded 6 wt-% SBA-15 exhibits optimal pervaporation desulfurization performance with a permeation flux of 22.07 kg·m⁻²·h⁻¹ and an enrichment factor of 6.76. Moreover, the detailed structure and properties of hybrid membranes are systematically characterized. This study demonstrates the immense potential of hierarchical porous materials as additives in membranes to simultaneously increase permeability and permselectivity.     

Synthesis and characterization of SBA-15 modified with alkali metals

A synthesis protocol that has not been previously reported in the literature that allows doping a solid of SBA-15 with alkali metals, preserving the structural features of the mesoporous solid has been developed. X-ray diffraction at low angles, Nitrogen adsorption, Electron transmission microscopy, X-ray photoelectron spectra, atomic absorption spectroscopy and Thermal Programmed Desorption of carbon dioxide were used to characterize the solids obtained. The introduction of alkali metals within the channels of the solid generates basic sites of weak and intermediate strength, which do not exist in undoped SBA-15. Without significant changes in the structural and textural properties of the support, only the densification of the channel walls is evidenced. According to the alkali metal used, the order established by the total number of sites obtained is: Li-SBA-15 ? K-SBA-15 ≈ Cs-SBA-15, while the order by force of both types of sites (weak and intermediate) is: Li-SBA-15 > Cs-SBA-15 > K-SBA-15.     

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。     

SBA-15的改性及催化文冠果油制备生物柴油

以介孔分子筛SBA-15为载体,采用直接合成法和后合成法镀饰Al后再负载碱金属盐KNO₃,制得负载型固体碱催化剂KNO₃-AlSBA-15和KNO₃-Al-SBA-15。用XRD、BET、SEM以及CO₂-TPD对催化剂进行表征。结果表明：在SBA-15上镀饰Al可以保护分子筛的介孔结构;进一步负载KNO₃,能够增强催化剂的碱性。将其应用于催化文冠果油酯交换制备生物柴油,结果显示催化剂KNO₃-Al-SBA-15的催化活性最好,优于传统均相催化剂,所得生物柴油产率可达92%,重复使用多次仍具有较好的催化效果。     

聚噻吩/SBA-15的合成与表征

以FeC l3为氧化剂,采用原位化学聚合的方法制备了聚噻吩/SBA-15新型复合材料,并对其结构和性能进行了表征。结果表明,小角X射线衍射和氮气吸附与脱附说明复合材料具有规则的介孔结构并且孔径明显小于分子筛SBA-15的孔径,红外光谱分析进一步证明PT进入了SBA-15的介孔孔道内,热重分析表明,聚噻吩进入孔道之后热稳定性得到了提高。     

吡啶基聚合离子液体的制备及其对油中噻吩硫的吸附性能

以4-乙烯基吡啶（VP）和1,4-对二氯苄（PXDC）为原料,通过自由基聚合和季铵化交联反应,制得了一种高度交联的离子液体聚合物--PVP-PXDC。采用凝胶渗透色谱法、元素分析法、红外光谱分析法、扫描电镜、热重分析及比表面积分析等分析方法对离子聚合物的组成、结构、形貌、热稳定性及比表面积、孔结构参数等进行了表征,并考察了吸附剂的脱硫性能。结果表明,先通过聚合得到重均分子量16万以上的PVP线性聚合物,再在DMF溶剂中按VP与PXDC摩尔比2：1加入交联剂,可得到平均孔径为17.8 nm聚合离子液体介孔材料,其热分解温度在250℃以上,比表面积为56.9 m²·g^-1。在油/剂质量比50：1和30℃条件下,其对1000 mg·kg^-1模型油中二苯并噻吩（DBT）、苯并噻吩（BT）和噻吩（T）的吸附量分别为5.65、5.48和4.53 mg S·g^-1,远高于常规吡啶基离子液体,吸附等温线符合Freundlich方程。     

KOH／SBA-15负载型固体碱催化剂的合成、表征及催化性能

采用后合成法制备出固体碱催化剂KOH／SBA-15,利用X射线衍射法（XRD）、N2吸附-脱附（BET）、透射电镜（TEM）、化学吸附剂表面碱性测定（COz—TPD）等对其进行表征。考察了其在大豆油酯交换反应制备生物柴油中的催化性能。结果表明,在相同反应条件下,与CaO／SBA-15和MgO／SBA-15相比,KOH／SBA-15在催化活性和孔扩散上都具有较大的优越性,催化制备生物柴油产率最高（83．56％）。     

SBA-15改性石墨烯环氧复合涂层制备及其防腐性能

用γ-氨丙基三乙氧基硅烷（KH-550）将SBA-15分子筛接枝到石墨烯上制备功能填料，并将其填充到水性环氧树脂中制备复合涂层。采用红外光谱（FTIR）、氮气吸附脱附和透射电镜（TEM）对填料进行表征；采用电化学阻抗谱（EIS）、盐雾试验和附着力测试等方法对不同填料添加量涂层的防腐性能及力学性能进行表征。实验结果表明，当功能填料添加质量为1.0%时，涂层具有最佳的电化学性能、耐盐雾性能、以及附着力性能。复合涂层的防腐性能明显优于纯环氧涂层，因为功能填料的孔/片协同结构有效的延缓了腐蚀粒子到达金属基材表面的时间。     

V/SBA-15的水热合成法制备及其催化氧化性能研究

为了制备负载型介孔分子筛V/SBA-15并研究其在乙苯制苯乙酮反应中的催化性能,以P123(三嵌段共聚物)为模板剂,正硅酸乙酯为硅源,柠檬酸氧钒配合物为前驱体,在酸性条件下采用水热法一步合成了V/SBA-15有序介孔材料,利用XRD,BET,FT-IR等手段对所合成的V/SBA-15材料进行了结构表征,并在乙苯制苯乙酮反应中以苯乙酮选择性和收率来验证催化剂的催化性能。实验结果表明:此合成材料具有类似于SBA-15的高度有序的六方介孔结构,活性组分钒均匀分散在介孔氧化硅基体中;在催化氧化乙苯制苯乙酮反应的优化条件下,苯乙酮选择性和收率分别为80.87%,35.26%。     

High performance sorbents for diesel oil desulfurization

Sorbents with different Ni loading supported on silica–alumina (SiAl) and activated carbon (AC) were synthesized and tested for removal of sulfur compounds from a model diesel oil, containing nearly 250 ppmw S as benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). A state-of-art Commercial Ni-based sorbent and two Norit activated carbons were also tested for comparison. Moreover, the influence on sorbents uptake capacity of the presence of aromatics in amounts representative of real diesel oils was studied. Both commercial and home-made materials performed worse in presence of aromatic compounds. Probably, the latter competed with the refractory sulfur compounds (DBT and 4,6-DMDBT) in the adsorption on active sites. As a first important result of the investigation the sorbents carrying 45% and 30% of Ni on SiAl showed a breakthrough uptake capacity of nearly, respectively, 2 and 2.6 times higher than Commercial sorbent as a consequence of their higher Ni dispersion and surface area. Moreover, activated carbons and the sample with 28%Ni on AC showed an even higher breakthrough uptake capacities. In particular, the deposition of nickel on activated carbon is an innovative approach which takes advantage of the selectivity of Ni towards S-species and the high adsorptive capacity of AC support.     

Synthesis and characterization of the SBA-15/carbon cryogel nanocomposites

The ordered mesoporous silica SBA-15 materials were synthesized using Pluronic P123 (non-ionic triblock copolymer, EO₂₀PO₇₀O₂₀), under acidic conditions. SBA-15/carbon cryogel composites were obtained by sol–gel polycondensation of resorcinol and formaldehyde followed by freeze drying, and subsequent pyrolysis, in the presence of different amounts of SBA-15. For comparison purpose, SBA-15/carbon composite was also prepared using sucrose as carbon source. These materials were characterized by room temperature nitrogen adsorption–desorption measurement, X-ray diffraction, scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. It was revealed that the samples have amorphous structure, high specific surface area (350–520 m² g^?1) and developed meso- as well as microporosity. The porosity of structure depends on the carbon source and Si/C ratio which can be easily controlled by varying concentration of starting solution.     

HPWA/SBA-15催化合成对叔丁基苯酚

以SBA-15负载磷钨酸（HPWA）为催化剂、甲基叔丁基醚（MTBE）和苯酚为原料在钢密封间歇反应釜中进行催化合成对叔丁基苯酚的实验研究。考察了HPWA负载量、催化剂用量、反应温度、反应时间及原料配比对烷基化反应的影响。实验结果表明,反应温度为160 ℃、负载HPWA质量分数30%、反应时间3 h、催化剂用量为原料质量的5%和原料配比n(MTBE)∶n(苯酚)＝2∶1时,苯酚的转化率为85.1%, 对叔丁基苯酚的选择性66.87%。实验中HPWA/SBA-15分子筛表现出较高的活性及选择性。     

HPWA/SBA-15催化合成2-叔丁基对甲酚

以SBA-15负栽磷钨酸(HPWA)为催化剂,甲基叔丁基醚(MTBE)和对甲酚为原料,在小型固定床反应器上进行了合成2-叔丁基对甲酚的试验研究,试验考察了HPWA负载量、反应温度、反应空速及原料配比对反应转化率、选择性的影响.试验结果表明,经HPWA改性后SBA-15的酸性增强,对甲酚转化率增大.适宜的反应条件为,反应温度160 ℃,HPWA负载量40%,空速3.0 h-1,原料MTBE和甲酚摩尔比为1.5.在适宜的条件下,对甲酚的转化率65.87%,2-叔丁基对甲酚的选择性97.81%.