Oxidative Desulfurization of Fuel Oil at Room Temperature Catalyzed by Ordered Meso-macroporous HPW/SiO_2

A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO_2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N_2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO_2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.     

Three-dimensionally Ordered Macroporous Phosphotungstic Acid/SiO_2 for Efficient Catalytic Oxidative Desulfurization

Three-dimensionally ordered(3DOM) macroporous phosphotungstic acid/SiO_2(HPW/SiO_2) materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization(ODS) of the model fuel oil. The obtained HPW/SiO_2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N_2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO_2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene(DBT) could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.     

HPW/SBA-15的制备及其催化氧化脱硫性能研究

以SBA-15分子筛为载体、磷钨杂多酸（HPW）为活性组分,制备磷钨酸负载型催化剂.以HPW/SBA-15为催化剂、双氧水为氧化剂对模拟柴油进行催化氧化脱硫研究,考察磷钨酸负载量、反应时间、温度和剂油比对脱硫率的影响,得到了优化的催化氧化条件：磷钨酸负载量为30%,反应温度80℃,反应时间60min,剂油比1︰6时,脱硫率可达97.8%.     

Three-dimensionally Ordered Macroporous Phosphotungstic Acid/SiO<Subscript>2</Subscript> for Efficient Catalytic Oxidative Desulfurization

Three-dimensionally ordered (3DOM) macroporous phosphotungstic acid/SiO₂ (HPW/SiO₂) materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization (ODS) of the model fuel oil. The obtained HPW/SiO₂ materials were characterized through scanning electron microscopy, powder X-ray diffraction, N₂ sorption, and Fourier transform infrared spectroscopy. The results indicated that 3DOM HPW/SiO₂ possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene (DBT) could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.     

固载杂多酸盐催化剂TiSiW12O40／TiO2催化合成DOP的研究

用自制的固载杂多酸催化剂ＴｉＳｉＷ１２Ｏ４０／ＴｉＯ２催化合成邻苯二甲酸二异辛醌（ＤＯＰ）,结果表明该固载杂多酸催化剂对酯化合成ＤＯＰ具有催化活性高,催化剂易于回收并可多次重复使用,不污染环境等优点。讨论原料配比,酯化时间,催化剂用量及其重复使用次数对醌化率的影响。     

在 Li_2SO_4·Fe_xO_y/TiO_2催化剂上的甲烷氧化偶联

在一个常规固定床流动体系,对甲烷氧化偶联合成乙烯、乙烷反应的催化剂进行了广泛的研究。提出了一种新的催化剂,较好地解决了以前存在的催化剂易失活及不适合催化较高分压的甲烷反应气问题。使用2克该催化剂,在常压、1103K,CH_4:O_2:N_2=20:8:20ml/min 的反应条件下,连续反应32小时后,C_2产率和选择率仍分别保持在31.4%和81.1%以上。     

固体超强酸催化非均相酯化反应的动力学

结合固体超强酸催化剂的结构特点 ,研究了乙酸与正丁醇进行非均相催化酯化反应的动力学方程。通过不同温度下酯化反应实验得到的动力学参数发现 ,酯化反应在固体超强酸催化剂作用下为脱附反应所控制的二级可逆反应 ,反应活化能为 42 .2 9k J· mol- 1,频率因子 k0 为 3.0 1 7× 1 0 3( mol· L- 1· min) - 1,确定了动力学方程 ,验证了反应机理推导的可靠性     

TiO_2/NiO复合纳米纤维制备及光催化性能研究

通过溶胶-凝胶过程,采用静电纺丝技术,以聚乙烯吡咯烷酮（PVP,Mn=900 000）和钛酸正丁酯为前驱物,制备了PVP/Ti（OPr）4/Ni（CH3COO）2复合一维纳米纤维材料。经控温缓慢氧化分解,在600℃的条件下成功制备了直径50～100 nmTiO2/NiO纳米纤维。采用扫描电镜、红外光谱、X射线粉末衍射、拉曼等分析手段对样品进行了表征,系统地介绍了TiO2光催化作用机理并在紫外灯下使用样品对罗丹明B溶液进行降解实验。结果显示,0.5%TiO/NiO复合纳米纤维具有良好的光催化活性。     

NiO对Au/TiO2催化甲醇水蒸汽重整制氢性能的影响

采用沉积沉淀方法制备了一系列Au—NiO／TiO2催化剂,考察了助剂NiO的加入量、焙烧温度对催化活性的影响。研究表明：助剂NiO的加入可以明显提高Au—NiO／TiO2催化甲醇水蒸汽重整制氢的活性;Au与NiO的配比存在最佳值,当Au负载量（质量分数）为2％,Au与NiO的质量比为1：5时,催化效果最佳;2％Au-10％NiO／TiO2催化剂的催化活性随焙烧温度的升高而降低。     

Oxidative Desulfurization of DBT with H_2O_2 over 3DOM H_3PW_(12)O_(40)/Al_2O_3 Catalyst

A series of heteropoly acid (HPA) based Al_2O_3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observed by scanning electron microscope (SEM) and transmission electron microscope (TEM).Mesopores could be detected by N_2 adsorption-desorption isotherms which further confirmed the 3DOM structural characteristics of catalyst.Moreover,Keggin-type HPW was highly dispersed in the Al_2O_3 framework,which suggested by powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) results.The oxidation desulfurization (ODS) performance of 3DOM H_3PW_(12)O_(40)/Al_2O_3 of refractory sulphur compounds was evaluated in the presence of hydrogen peroxide.It oxidized 98.5% of dibenzothiophene (DBT) into corresponding sulfone within 3 h,which exhibited superior ODS performance than corresponding mesoporous and microporous H_3PW_(12)O_(40)/Al_2O_3 catalyst.The enhancement of ODS efficiency is related to the improvement of mass transfer of DBT in the pore channel resulting from the interconnected 3DOM structure.Furthermore,the as-prepared catalyst still demonstrates outstanding cycle performance after 6 runs,which could be easily recovered from the model fuel.     

铁系元素对Mn/TiO_2催化剂低温SCR性能的影响

采用浸渍法制备了铁系元素(Fe、Co、Ni)掺杂的Mn/TiO2低温脱硝催化剂,考察了其在80~180℃范围内的脱硝催化效果,并通过XRD、BET、TG、H2-TPR和XPS等测试手段,对催化剂的物理化学性质进行了表征。结果表明,铁系元素的掺入对催化剂表面元素的分布、孔结构、物相组成等有不同的影响,可以明显改善Mn/TiO2催化剂的脱硝性能,在180℃时,分别可以达到97.21%(Fe-Mn/TiO2)、94.01%(Co-Mn/TiO2)、94.03%(Ni-Mn/TiO2)的NO转化效率。     

WO3/ZrO2固体超强酸催化氧化柴油深度脱硫研究

采用WO3/ZrO2固体超强酸作为催化剂,研究了H2O2/WO3/ZrO2体系催化氧化柴油深度脱硫性能,考察了氧化剂用量、催化剂用量、反应温度、反应时间等工艺参数对脱硫率的影响;在此基础上,引入功率超声进一步强化反应,并考察了超声频率、超声功率、超声时间等因素对脱硫效果的影响.实验结果表明,在反应温度60℃,反应.时间90min,氧化剂加入量V(H2O2):V(柴油)=1:10,催化剂用量15g/L柴油的最佳氧化脱硫条件下,氧化柴油经萃取后脱硫率可达91.0%.超声强化后,氧化反应时间缩短为40min,柴油脱硫率提高至95.6%.     

Fe—P—O催化剂上甲烷氧化偶联反应制C2烃

研究了较低温度（６５０℃左右）下,在Ｆｅ－Ｐ－Ｏ进行甲烷氧化制Ｃ２烃催化反应。考察了反应温度、催化剂配比等因素对该催化剂催化性能的影响,并对该体系催化剂进行ＸＲＤ、ＦＴＩＲ、ＸＰＳ表征分析,初步探讨了该催化反应的机理。结果表明,该催化剂具有较好的催化活性和稳定性,催化剂在反应过程中有新物相生成,并对反应具有促进作用。     

粘结组分对脱硫剂脱硫性能及机械强度的影响

以Al2O3、HNO3 等为粘结组分,ZnO 为储硫物质,Ni为活性成分,采用等体积浸渍法制备了Ni/ZnO 吸附脱硫剂。通过改变制备时粘结组分中的拟薄水铝石和硅藻土的质量比、硝酸用量、拟薄水铝石与硅藻土的总加 入量和载体混捏时间,考察了粘结组分对吸附脱硫剂活性及机械强度的影响。结果表明,随胶溶剂硝酸、拟薄水铝 石和硅藻土的总加入量增多,吸附脱硫剂脱硫性能提高,随载体中拟薄水铝石与硅藻土加入质量之比增大,吸附脱 硫剂脱硫性能先提高后降低存在最优值,随载体混捏时间增长吸附脱硫剂脱硫性能先提高后趋于稳定;随载体中拟 薄水铝石与硅藻土加入质量之比提高,加入胶溶剂硝酸减少,拟薄水铝石与硅藻土的总加入量增大,吸附脱硫剂机 械强度提高。     

硼改性TiO_2纳米管阵列负载Mo-Ni-P催化剂的制备及加氢脱硫性能

采用阳极氧化法制备适宜孔容和大比表面积的TiO2纳米管阵列,以其为载体将具有催化加氢活性的金属Mo和Ni负载其表面。通过负载前硼改性、磷修饰等手段制备了具有较大孔径(72.3nm)和比表面积(156m2/g)的催化加氢精制催化剂,并对其进行表征。催化加氢脱硫性能选用5mL固定床小试设备,以孤岛焦化柴油作为原料进行加氢评价。结果表明,压力7MPa,温度360℃,空速1.5h-1,氢油体积比为600∶1的条件下,该柴油产品脱硫率为96.6%,基本达到工业化生产的要求。     

负载型V_2O_5-WO_3/TiO_2/堇青石脱硝催化剂的研制及性能

以TiO2/堇青石蜂窝陶瓷为载体,V2O5-WO3为活性组分,采用静态浸渍的方法制备了用于氨法选择性催化还原烟气中NO的SCR催化剂,通过XRD和BET对催化剂进行了表征,并考察了该催化剂的应用性能。考察了制备方法、温度、NO浓度、空速和NH3/NO对SCR反应的影响。结果表明,活性组分浸渍溶液中添加助溶剂对制备的催化剂活性有一定的影响,主要影响催化剂表面V2O5的聚集形态,导致脱硝活性下降;活性组分浸渍溶液中添加助溶剂时,可显著提高催化剂的脱硝活性,在反应温度为375℃、NH3/NO=1、空速为10 000h-1的条件下,所制备的催化剂的NO脱除率最高,可达99%。     

低温混合碳四在SO_4~(2-)/TiO_2/HZSM-5催化剂上的芳构化反应

采用浸渍沉淀法制备了SO42-/TiO2/HZSM-5固体酸催化剂。通过对混合碳四在SO42-/TiO2/HZSM-5固体酸催化剂上的低温芳构化反应的研究,考查了二氧化钛的质量分数、硫酸浸渍浓度、硫酸浸渍时间、液固质量比、粘和剂的质量分数、沉淀老化温度和焙烧温度等催化剂的制备条件以及空速对反应的影响。结果表明,粘合剂的质量分数和硫酸浸渍浓度对催化性能有较大影响。粘合剂γ-Al2O3在质量分数为30%时催化性能最好;低的体积空速有利于提高BTX(苯、甲苯、二甲苯)和芳烃的选择性;此外,同ZnNi/HZSM-5催化剂相比,达到相近的BTX和芳烃的收率,SO42-/TiO2/HZSM-5催化剂可使反应温度降低140℃左右。     

Highly Efficient Synthesis of Environmentally Friendly Ag-modified TiO_2 Nanoflowers to Enhance Photocatalytic Performance

Ag-modified TiO_2 nanoflowers were prepared using a two-step process. The experimental process is green and free from contamination and can be synthesized directly at room temperature. Compared with pure TiO_2, Ag-modified TiO_2 enhances the absorption of visible light and effectively promotes the detachment of photoelectron pairs, Ag-TiO_2 has a significantly enhanced visible light response activity to photodecomposition of methyl orange(MO). It is shown that the strong interaction between Ag nanoparticles and TiO_2 enhances the photocatalytic activity of TiO_2 nanoflowers. The self-made open-air reactor was used to test the photocatalytic performance of different samples. The results showed that Ag-modified TiO_2 nanoflowers had excellent photodegradation ability. After repeated photodegradation of MO, Ag-modified TiO_2 nanoflowers showed good stability.     

多金属氧酸盐催化剂[(CH_3)_3NCH_2CH_2OH]_5PV_2Mo_(10)O_(40)的制备及其氧化脱硫性能研究

利用氯化胆碱通过沉淀的方法合成了多金属氧酸盐催化剂[(CH3)3NCH2CH2OH]5PV2Mo10O40,并通过红外光谱仪、X-射线粉末衍射仪以及元素分析仪等对其进行了表征.用氧气作为氧化剂,对模型燃料油中的二苯并噻吩(DBT)进行了在脱硫反应中催化氧化性能的研究.此外,该多酸盐催化剂在本催化体系中可以重复使用.     

C_OFe_2O_4催化PMS降解甲基橙的实验

采用溶胶凝胶法制备了磁性催化剂铁酸钴(C_OFe_2O_4),借助于X射线衍射(XRD)、扫描电子显微镜(SEM)、BET比表面积、磁滞回线(VSM)等手段对催化剂进行表征。以甲基橙溶液模拟染料废水,开展了C_OFe_2O_4催化活化过一硫酸氢钾(PMS)降解甲基橙的实验研究。考察了催化剂用量、PMS的浓度、溶液初始p H、反应温度对甲基橙降解效率的影响,得到了反应的最佳条件。当C_OFe_2O_4浓度为0.16 g/L,PMS浓度2.3 mmol/L,溶液初始pH为3,反应温度为25℃时,甲基橙的降解效率可达89.96%。通过查阅相关文献及X射线光电能谱分析(XPS)推测了甲基橙的降解机理。