B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应中的溶剂效应

 采用不同极性的溶剂作为环己酮肟的溶剂,考察了溶剂极性对B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应性能的影响. 结果表明,除乙醇外,随着溶剂极性的增大,己内酰胺的收率逐渐提高. 在所考察的溶剂范围内,当采用极性最强的乙腈为溶剂时,B2O3/TiO2-ZrO2的催化性能最佳,连续反应9 h,环己酮肟的转化率为100%,己内酰胺的选择性高达98.6%. 极性较强的溶剂可显著改善B2O3/TiO2-ZrO2催化性能的原因主要是其有利于反应所生成的己内酰胺从催化剂表面快速脱附,从而可抑制己内酰胺进一步发生聚合及分解等副反应.     

环己酮肟在B2O3/Al2O3-TiO2催化剂上的气相Beckmann重排反应

制备了B2O3/Al2O3-TiO2复合载体催化剂,并考察了其对环己酮肟气相Beckmann重排制己内酰胺反应的催化性能. 结果表明,载体中TiO2的含量、B2O3的负载量、载体的预处理温度及催化剂的焙烧温度等均对催化剂的性能产生明显的影响. 当载体中TiO2含量为60%,B2O3负载量为20%,催化剂经350 ℃焙烧时,环己酮肟的气相Beckmann重排反应的转化率和选择性很高. 用BET,NH3-TPD,XRD和IR等方法对催化剂的织构、表面酸性和晶相等进行了表征,并与催化剂的活性进行了关联,表明催化剂表面中等强度的酸中心浓度与催化剂的选择性具有对应关系.     

V2O5-CeO2/TiO2-ZrO2催化剂表征及NH3还原NOx性能

商业选择性催化还原(SCR)催化剂V2O5-WO3(MoO3)/TiO2存在反应温度窗口窄(300–400 oC)和SO3转化率高等缺点,同时占催化剂总质量80%以上的载体TiO2比表面积小,热稳定性差.已有研究发现TiO2-ZrO2固溶体具有较大的比表面积和较强的表面酸性, TiO2与ZrO2的摩尔比为1：1时其比表面积达到最大. CeO2作为SCR催化剂的组成部分,由于其优良的储氧和放氧能力受到广泛关注.研究表明, CeO2-CuO, Ce/Ti-Si-Al和Mo2O3(Co2O3)/Ce-Zr等催化剂具有优良的SCR脱硝活性,同时对V2O5-WO3/TiO2催化剂进行CeO2改性,可提高催化剂的抗SO2中毒能力.实际烟气组分中同时存在SO2和H2O,必定会导致催化剂硫酸盐中毒,而目前对含Ce催化剂的硫酸盐中毒情况研究较少,因此开发新型高效脱硝催化剂十分必要.前期我们研究了xCeO2-3%V2O5/TiO2-ZrO2催化剂,发现CeO2可以显著拓宽脱硝温度窗口,同时增强催化剂酸性位点,但是V2O5含量较高时对环境及人体健康均有较大危害.本文采用共沉淀法制备摩尔比为1：1的TiO2-ZrO2固溶体,用浸渍法负载不同摩尔比的CeO2和1%的V2O5,得到一系列V-xCe/Ti-Zr催化剂,结合X射线衍射(XRD)、比表面积测试(BET)、高分辨透射电镜(HRTEM)、程序升温还原(H2-TPR)、原位漫反射红外光谱(in situ DRIFTS)和程序升温脱附(NH3-TPD)等手段分析催化剂的晶相、活性物质分散程度、氧化还原性质及表面酸性,在200–450 oC范围内考察Ce掺杂催化剂选择性催化还原NOx的脱硝活性,并在250 oC测试催化剂在NH3+NO+O2+SO2+H2O气氛中的脱硝活性,研究催化剂抗硫酸盐中毒能力.研究发现,CeO2掺杂可以拓宽脱硝反应活性窗口, V-0.2Ce/Ti-Zr (摩尔比Ce：Ti =0.2)表现出最优的脱硝性能,在250–350oC范围内脱硝效率均在92%以上,同时与前期研究结果对比发现CeO2含量较高时会导致高温段NOx转化率下降. XRD和HRTEM结果表明,ZrO2的添加可以显著降低载体TiO2的结晶度,复合氧化物TiO2-ZrO2呈无定形态, CeO2高度分散于载体之上,并且催化剂以单晶形式存在. H2-TPR结果表明,CeO2能显著提高催化剂的还原能力,主要的还原反应发生在CeO2的α(200–430oC)和β(430–600 oC)还原峰上,总体而言, V-0.2Ce/Ti-Zr表现出最大的氢气消耗量,即其还原性最强.低V2O5负载有利于较低温度SCR反应, V-0.3Ce/Ti-Zr的钒氧化物还原峰强度最大,其次是V-0.2Ce/Ti-Zr. NH3-TPD测试发现V2O5/TiO2主要存在中强酸及强酸,而V2O5/TiO2-ZrO2主要是弱酸, CeO2负载后随着其含量提高,弱酸强度增加.结合氨气原位漫反射红外光谱发现, CeO2可以增加催化剂Br?nsted和Lewis酸位数量,同时出现反应中间物–NH2, V2O5的负载量较高会抑制1660 cm–1处Br?nsted酸吸收峰的出现. BET结果发现, TiO2-ZrO2和V2O5/Ti-ZrO2比表面积分别可达255.73和143.77 m2/g, V2O5/TiO2仅为66.1 m2/g,表明ZrO2的添加可以显著增大催化剂比表面积,进而有利于SCR反应进行,沉积的氧化物进入载体孔道导致催化剂比表面积降低. V2O5-xCeO2/TiO2-ZrO2表现出较强的抗SO2中毒能力,但是在H2O存在条件下脱硝活性较差,可能是生成的硫酸铵盐及亚硫酸盐阻塞催化剂孔道所致. SO2和H2O停止通入后, V2O5-0.3CeO2/TiO2-ZrO2活性恢复至原有水平, V2O5-0.2CeO2/TiO2-ZrO2恢复至最初的84%.对中毒催化剂进行不同反应温度下的活性测试,发现V2O5-0.2CeO2/TiO2-ZrO2在中温段反应活性显著降低,可能是由于Ce(SO4)2的形成所致,由于V2O5-0.3CeO2/TiO2-ZrO2的Ce含量较高,其在此温度范围内活性依旧较高.两者在高温段NOx转化率均较高,推测是V2O5开始发挥活性组分作用的缘故.     

B2O3／TiO2—ZrO2催化环己酮肟气相Beckmann重排反应研究Ⅳ.TiO2—ZrO组成的影响

采用共沉淀法制备了不同组成的复合氧化物TiO2-ZrO2.N2吸附和差热分析结果表明，随着TiO2-ZrO2中TiO2含量的增加，其BET比表面积和晶化温度提高，并均在TiO2含量为50％时达到最大值，以TiO2-ZrO2为载体的B2O3／TiO2-ZrO2催化剂对环己酮肟气相Beckmann重排反应的催化性能表明，随着TiO2-ZrO2中TiO2含量的增加，己内酰胺的收率逐渐升高，当TiO2含量增加至50％时，收率达到最大值（96．7％），之后随着TiO2含量的进一步增加，己内酰胺的收率逐渐降低。     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅲ. 反应条件的影响

 对B2O3／TiO2－ZrO2催化环己酮肟气相Beckmann重排制己内酰胺的反应条件进行了优化研究，系统考察了反应温度、原料空速、载气及其流速和稀释剂等对催化剂催化性能的影响．结果表明，当反应温度为300℃、环己酮肟的重时空速WHSV）为0．33h－1、氮气为载气（流速30ml／min）及乙腈为稀释剂时，B2O3／TiO2－ZrO2催化剂的催化性能最佳，连续反应6h，环己酮肟的转化率为100％，己内酰胺的选择性高达98．6％．     

V2O5/TiO2-ZrO2催化剂上甲醇选择氧化制甲缩醛

采用共沉淀法制备TiO2-ZrO2复合氧化物载体、等体积浸渍法制备V2O5/TiO2-ZrO2催化剂,对催化剂在温和条件下甲醇选择氧化生成甲缩醛(DMM)反应进行研究.结果表明,与单一氧化物载体TiO2或ZrO2负载的钒基催化剂相比,V2O5/TiO2-ZrO2对甲醇选择氧化具有较好的催化性能.XRD、NH3-TPD和...     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究Ⅱ.焙烧温度的影响

采用XRD、FT-IR和NH3-TPD等方法，研究了载体预焙烧温度和催化剂活化焙烧温度对B2O3/TIO2-ZRO2催化剂的结构、酸性和催化环己酮肟气相Beckmann重排反应性能的影响。结果表明，在383-773K范围内，载体预烧温度对催化剂性能的影响不大，但经973K高温预焙烧后，由于生成了ZrTiO4晶相，使其与H3BO3的相互作用减弱，从而导致催化剂的酸性和反应性能降低，提高催化剂活化焙烧温度，有利于B2O3与TiO2-ZrO2的相互作用，生成更多的Beckmann重排反应所需的中等强度酸中心，使催化剂的活性和选择性提高；但活化焙烧温度过高，会使催化剂中大量的B2O3晶粒析出，引起酸中心数量和催化活性的明显下降。     

环已酮肟在B2O3／Al2O3—TiO2催化剂上的气相Beckemann重排反应

制备了B2O3/Al2O3-TiO2复合载体催化剂,并考察了其对环已酮肟气相Beckemann重排制已内酰胺反应的催化性能。结果表明,载体中TiO2的含量、B2O3的负载量、载体的预处理温度及催化剂的焙烧温度等均对催化剂的性能产生明显的影响。当载体中TiO2含量为60%,B2O3负载量为20%,催化剂经350℃焙烧时,环已酮肟的气相Beckemann重排反应的转化率和选择性很高。用BET,NH3-TPD,XRD和IR等方法对催化剂的织构、表面酸性和晶相等进行了表征,并与催化剂和活性进行了关联,表明催化剂表面中等强度的酸中心浓度与催化剂的选择性具有对应关系。     

TiO_2柱层状HTiNbO_5的合成及在环己酮肟气相Beckmann重排反应中的催化性能

钛酸异丙酯(TIP)、CH3COOH和H2O按体积比1∶16∶40混合后得到Ti(Ⅳ)多聚阳离子柱化液,与正癸胺插层钛铌酸盐进行交换反应后制得钛(Ⅳ)多聚阳离子插层钛铌酸盐,其层间距为1.70 nm.在空气气氛中于623 K焙烧处理后,所得产品能保持良好的层柱结构.在空气气氛中于723 K焙烧后所得的TiO2柱层状钛铌酸(TiO2-HTiNbO5),其层间距为0.97 nm,比表面积为89 m2/g.以TiO2-HTiNbO5为载体,用浸渍法制备了一系列B2O3负载量不同的负载型样品B2O3/TiO2-HTiNbO5,考察了它们在环己酮肟气相Beckmann重排反应中的催化性能并测试了它们的红外光谱.B2O3/TiO2-HTiNbO5的催化性能优于TiO2-HTiNbO5.在B2O3负载质量分数为7.31%的催化剂上,环己酮肟转化率接近100%且在4.5 h内无明显改变,己内酰胺选择性接近90%.红外光谱分析结果表明,当B2O3负载量很低时,硼组分高度分散于载体TiO2-HTiNbO5表面,并主要以BO4结构形式存在;当B2O3负载质量分数高于7.31%时,BO3结构形式在数量上占优势.将催化性能与红外光谱结果关联后可知,对于负载型样品B2O3/TiO2-HTiNbO5,表面的BO3和BO4两种结构形式在环己酮肟气相Beckmann重排反应中具有协同促进作用.     

以胶原纤维为模板制备多孔纤维状SO_4~(2-)/TiO_2-ZrO_2固体酸及其酯化催化性能

本文以胶原纤维为模板,制备了多孔纤维状TiO2-ZrO2复合氧化物,并以此为载体制备了多孔纤维状SO42-/TiO2-ZrO2固体酸。SEM观察发现TiO2-ZrO2和SO42-/TiO2-ZrO2均复制了胶原纤维独特的纤维结构,TiO2-ZrO2氧化物的比表面积达到77.51 m2·g-1;XRD分析发现,Ti-Zr摩尔比对TiO2-ZrO2的晶相结构有重要影响,当Ti/Zr摩尔比为0.67∶1时,TiO2-ZrO2以TiZrO4晶相为主;NH3-TPD分析表明SO42-/TiO2-ZrO2的酸量及酸强度与Ti-Zr摩尔比以及活化温度有着密切关系。在乙酸与正丁醇的酯化反应中,多孔纤维状SO42-/TiO2-ZrO2固体酸表现出优良的催化性能。当催化剂用量为6.5wt%,反应时间为60min时,乙酸的转化率高达98.1%;该固体酸催化剂重复使用性优良,循环使用5次时,转化率仍然保持在85%以上。     

SO42-/TiO2-ZrO2复合氧化物固体酸催化剂的长叶烯芳构化催化性能

本工作用溶胶-凝胶法制备不同组成的SO42-/TiO2-ZrO2复合氧化物固体酸催化剂,用微型催化反应评价结合X-射线粉末衍射(XRD)、孔结构/BET表面积测试和NH3-程序升温脱附(NH3-TPD)等表征了SO42-/TiO2-ZrO2复合氧化物固体酸催化剂结构、表面酸性和长叶烯芳构化催化性能。复合氧化物固体酸SO42-/TiO2-ZrO2催化剂具有优良的长叶烯芳构化催化性能,并且其芳构化催化性能与催化剂组成和表面酸性密切相关。随催化剂中nZr/(nZr+nTi)增加,催化剂表面中等强度的酸中心量增加,芳构化产物选择性和收率明显增加,在nZr/(nZr+nTi)=0.5时达极大值。随nZr/(nZr+nTi)进一步增加,不仅催化剂表面酸中心量减少、原料转化率明显下降,而且催化剂酸强度增强,导致芳构化产物选择性和收率下降。催化长叶烯芳构化的二元复合氧化物固体酸SO42-/TiO2-ZrO2催化剂适宜的组成为nZr/(nZr+nTi)=0.5。     

The Effect of Platinum on Stability of the B2O3/TiO2-ZrO2 Catalyst for Beckmann Rearrangement of Cyclohexanone Oxime

It has been well illustrated that the rapid catalyst deactivation with time is the most serious limitation of vapor phase approach to the production of ε-caprolactam from cyclohexanone oxime (CHO) (Scheme 1), and is a common problem with all catalyst typ…     

Characterization and reactivity of copper oxide catalysts supported on TiO2-ZrO2

A series of copper catalysts supported on TiO2-ZrO2 with copper loading varying from 1.0 to 21.6 wt % were prepared by a wet impregnation method. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, electron spin resonance (ESR), temperature programmed reduction (TPR), and Brunauer-Emmett-Teller specific surface area measurements. Copper dispersion and metal area were determined by N2O decomposition by the passivation method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings <16.8 wt % in the sample and as a crystalline CuO phase at higher Cu loadings. Copper dispersion increases with Cu loading up to 5.1 wt % and levels off at higher loadings. The XPS peak intensity ratios of Cu 2p(3/2)/Ti 2p(3/2) and Cu 2p(3/2)/Zr 3d(5/2) were compared with the copper dispersion calculated from N2O decomposition. ESR results suggest the presence of two types of copper species on the TiO2-ZrO2 support. TPR profiles reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and related to the dispersion of Cu on TiO2-ZrO2.     

Methane reforming With CO2 to syngas over CeO2-promoted Ni/Al2O3-ZrO2 catalysts Prepared Via a direct sol-gel process

CeO2-promoted Ni/Al2O3-ZrO2 (Ni/Al2O3-ZrO2-CeO2) catalysts were prepared by a direct sol-gel process with citric acid as gelling agent. The catalysts used for the methane reforming with CO2 was studied by infrared spectroscopy (IR), thermal gravimetric analysis (TGA), microscopic analysis, X-ray diffraction (XRD) and temperature-programmed reduction (TPR). The catalytic performance for CO2 reforming of methane to synthesis gas was investigated in a continuous-flow micro-reactor under atmospheric pressure. TGA, IR, XRD and microscopic analysis show that the catalysts prepared by the direct sol-gel process consist of Ni particles with a nanostructure of around 5 nm and an amorphous-phase composite oxide support. There exists a chemical interaction between metallic Ni particles and supports, which makes metallic Ni well dispersed, highly active and stable. The addition of CeO2 effectively improves the dispersion and the stability of Ni particles of the prepared catalysts, and enhances the adsorption of CO2 on the surface of catalysts. The catalytic tests for methane reforming with CO2 to synthesis gas show that the Ni/Al2O3-ZrO2-CeO2 catalysts show excellent activity and stability compared with the Ni/Al2O3 catalyst. The excellent catalytic activity and stability of the Ni/Al2O3-ZrO2-CeO2 are attributed to the highly, uniformly and stably dispersed small metallic Ni particles, the high reducibility of the Ni oxides and the interaction between metallic Ni particles and the composite oxide supports.     

钛锆复合氧化物载体的制备、物化性质及在催化反应中的应用

 TiO2-ZrO2复合氧化物具有比TiO2和ZrO2更高的比表面积、更好的热稳定性和更强的表面酸碱性,作为催化剂载体已引起很大的研究兴趣并得到了重要的应用. 本文主要介绍了TiO2-ZrO2复合氧化物载体的制备方法以及织构、结构和表面酸碱性等物化性质,并对其在催化反应中的应用进行了综述.     

TiO2–ZrO2的表征及其异丙醇催化转化性能

用共沉淀法制备了TiO2-ZrO2复合氧化物. 采用N2吸附、XRD、TEM、NH3和CO2吸附量热、NH3吸附红外对TiO2-ZrO2体系的结构及酸碱性等进行了表征. 结果表明: 与单纯的氧化物相比, 形成的复合氧化物为无定形物相, 有介孔结构, 表面积明显提高, 可达218 m2·g-1; 初始吸附热差别不大, 但具有更多的表面B酸位; 随着TiO2掺入量的增大, 复合氧化物表面碱位减少. 异丙醇催化转化, 在无氧条件下, ZrO2、TiO2和TiO2-ZrO2复合氧化物上丙烯的选择性大于90%, 说明这些氧化物具有强的表面酸性; 在有氧条件下, ZrO2和TiO2丙酮的选择性达到70%～85%, 主要体现为氧化还原性; 而在复合氧化物上丙烯选择性增大到70％左右, 丙酮的选择性下降为30%左右, 表明生成的复合氧化物表面上的氧化还原性削弱, 酸性增强.     

Catalytic abatement of CO and volatile organic compounds in waste gases by gold catalysts supported on ceria-modified mesoporous titania and zirconia

Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6–Zr(OC3H7)4 assembly pathway, and ceria‐modified TiO2 and ZrO2, prepared by a deposi‐tion–precipitation (DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the cata‐lytic abatement of air pollutants, i.e., CO, CH3OH, and (CH3)2O. The gold was supported on the mes‐oporous oxides by a DP method. The supports and catalysts were characterized by powder X‐ray diffraction, high‐resolution transmission electron microscopy, N2 adsorption–desorption analysis, and temperature‐programmed reduction technique. A high degree of synergistic interaction be‐tween ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction be‐tween the gold nanoparticles and ceria‐mesoporous oxide supports. The gold catalysts supported on ceria‐modified mesoporous ZrO2 displayed superior catalytic activity (~100%conversion of CO at 10 °C and CH3OH at 60 °C). The high catalytic activity can be attributed to the ability of the sup‐port to assist oxygen vacancies formation. The studies indicate that the ceria‐modified mesoporous oxide supports have potential as supports for gold‐based catalysts.     

Li-Mn/WO_(3)/TiO_(2)固体酸催化剂的制备及其甲烷氧化偶联催化性能研究北大核心CSCD

Li-Mn/WO_(3)/TiO_(2)催化剂具有良好的低温OCM催化性能,采用浸渍法制备Li-Mn/WO_(3)/TiO_(2)催化剂,并详细考察WO_(3)对催化剂物理化学性质及催化性能的影响.利用X射线衍射(XRD)、CO_(2)程序升温脱附(CO_(2)-TPD)、O_(2)程序升温脱附(O_(2)-TPD)、H_(2)程序升温还原(H_(2)-TPR)、拉曼光谱(Raman)和X射线光电子能谱(XPS)等表征技术对催化剂进行了研究,发现WO_(3)的添加提高了C_(2)选择性,并有效抑制了深度氧化.XRD与CO_(2)-TPD结果表明,WO_(3)的添加不仅有利于金红石型TiO_(2)的形成而且能够中和催化剂表面的强碱位,从而抑制了深度氧化反应.O_(2)-TPD和H_(2)-TPR结果表明,WO_(3)的添加降低了晶格氧(O^(2-))移动性,进而提高了反应的C_(2)选择性.此外,WO_(3)的添加促使了低温氧化偶联活性物种MnTiO_(3)的形成并提高了活性物种的分散性,因此提高了催化剂甲烷氧化偶联的反应活性和选择性.所有Li-Mn/x%WO_(3)/TiO_(2)催化剂中,Li-Mn/5%WO_(3)/TiO_(2)催化剂显示出最佳的OCM反应性能.在750℃,CH_(4)∶O_(2)∶N_(2)=10∶4∶5,GHSV=2280 mL·g^(-1)·h^(-1)条件下,最高的C_(2)产物收率可达16.3%.     

Influence of ceria modification on the properties of TiO2-ZrO2 supported V2O5 catalysts for selective catalytic reduction of NO by NH3

TiO(2)-ZrO(2) (hereafter denoted as Ti-Zr) supported V(2)O(5) catalysts with different loadings of CeO(2) were synthesized, and their physicochemical properties were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), in situ Fourier transform infrared spectroscopy (in situ FT-IR) and temperature-programmed reduction (TPR). Their catalytic activities toward the NO(x) reduction reaction with NH(3) were tested. We found that with the addition of CeO(2), more NO was removed in a wide temperature range of 220-500 °C. As the CeO(2) content was increased from 10% to 20% (i.e., the molar ratio of Ce to Ti-Zr), NO conversion increased significantly; after that, increasing CeO(2) content, however, decreased NO conversion. In particular, the addition of CeO(2) to V(2)O(5)/Ti-Zr suppressed the coke deposition and rendered a stable and high catalytic activity. The characterization results indicated that: (1) the deposited vanadium and cerium oxides were highly dispersed over the Ti-Zr support, and in addition to ZrV(2)O(7), a common binary compound observed in V(2)O(5)/Ti-Zr, CeVO(4) and Ce(3)ZrO(8) was formed upon increasing CeO(2) content; (2) the introduction of CeO(2) to V(2)O(5)/Ti-Zr sample promoted the redox ability of the resulting catalysts; and (3) the Ce-containing catalysts possessed the greater amount of surface acidic and active intermediate.