十聚钨酸季铵盐催化苯甲醇合成苯甲醛的研究

研究了以十聚钨酸季铵盐为催化剂、30%过氧化氢为氧源催化氧化苯甲醇合成苯甲醛的反应,考察了不同催化剂的催化效果、反应温度、反应时间、十聚钨酸季铵盐的用量和过氧化氢的用量等对苯甲醇选择性催化氧化反应的影响。结果表明,以十聚钨酸季铵盐（[BunPy]4W10O32）为催化剂,在60℃,十聚钨酸季铵盐用量为0.08mmol,反应15h,30%过氧化氢用量为45mmol,苯甲醇的用量为30mmol时,苯甲醇的转化率为96.7%,苯甲醛的选择性达到91.5%。     

蒙脱土担载钴配合物催化剂制备及性能研究

制备了系列蒙脱土担载钴(Ⅱ)(Co(Ⅱ))配合物催化剂,并对其结构进行了X射线衍射和透射电镜等表征,初步研究了蒙脱土担载钴(Ⅱ)配合物催化剂对烯烃的催化氧化性能.结果表明:配体进入了蒙脱土的片层间与Co(Ⅱ)配位,形成蒙脱土担载的铜配合物复合催化材料;在催化剂催化H2O2氧化苯乙烯的反应中,对苯甲醛和环氧苯乙烷的选择性高达94.7%,转化率达到38.4%;在环己烯的氧化反应中,对环氧环己烷、环己醇、环己烯醇和环己烯酮的选择性共达到98.5%,转化率达到33.2%.     

CuO_x/4A催化剂上苯甲醇液相氧化制苯甲醛性能研究

采用等体积浸渍法制备了一系列Cu改性4A分子筛催化剂,用于过氧化氢液相催化氧化苯甲醇制苯甲醛的反应。采用N2等温吸附-脱附法、XRD和程序升温还原对不同负载量的CuOx/4A催化剂进行了表征。当苯甲醇20 mL、双氧水30 mL、催化剂0.2 g、反应温度80℃、反应时间5 h时,质量分数6%CuOx/4A催化剂上苯甲醇的转化率为49.5%,苯甲醛选择性为83.6%,苯甲醛收率为41.4%,反应活性最高;4A分子筛上Cu及Cu负载量的改变,显著影响着催化剂的比表面积、金属物相结构和还原性。6%CuOx/4A催化剂表现出较佳的催化氧化苯甲醇制苯甲醛性能,主要归因于4A分子筛上高分散的Cu-O物种;而且6%CuOx/4A催化剂具有较低的还原温度。     

催化湿式过氧化氢氧化法处理电镀废水中有机物的研究

以蒙脱土为载体,以AlCl_3·6H_2O、FeCl_3·6H_2O及NiCl_2·6H_2O为改性剂,采用离子交换法制备了一系列柱撑蒙脱土催化剂。将制备的催化剂用于催化湿式过氧化氢氧化法(CWPO)处理模拟电镀废水中的有机物。研究了Fe与Ni的物质的量比及金属负载量对催化剂性能的影响,并研究了工艺条件对COD去除率的影响。结果表明:当Fe与Ni的物质的量比为8∶2、金属负载量为7%时,制备的催化剂性能最优。催化反应工艺条件对COD去除率的影响较大。当反应温度为60℃、废水初始pH值为4、H_2O_2的浓度为30 mmol/L时,COD的去除率最高可以达到90%以上。     

Fe,Ce, Al-MMT催化剂制备及其性能研究

为解决催化剂制备耗水量大的问题,以钠基蒙脱土为载体,通过聚阳离子交换法在不同分散介质(水、乙醇)中制备铁,铈,铝-柱撑蒙脱土催化剂(Fe, Ce, Al-MMT)。以催化湿式过氧化氢氧化(CWPO)降解苯酚废水的COD去除率和Fe离子溶出量来评价催化剂的活性及稳定性,采用XRD、N_2吸附-脱附和SEM等表征技术分析催化剂的微观形貌和结构,并借助自由基捕获实验探究CWPO反应机理。结果表明:与水溶液中制备的催化剂相比,在乙醇中制备的Fe, Ce, Al-MMT(25%EtOH)具有更高的层间距(d_(001)为2.649 nm)、更大的比表面积(181.2 m~2/g)、活性组分分散更均匀。因此表现出更高的催化活性,对苯酚废水的COD去除率高达94.48%。Fe, Ce, Al-MMT(25%EtOH)催化剂具有良好的稳定性,在5次催化循环后COD去除率仅下降6%,活性组分Fe离子溶出量仅为0.047 3 mg/L。     

CaO/La2O3固体碱催化剂制备及其催化大豆油酯交换反应性能

采用共沉淀法制备了氧化钙/三氧化二镧（CaO/La2O3）固体碱催化剂,并将其应用于大豆油与甲醇进行的酯交换反应。XRD表征结果表明,活性组分在三氧化二镧上高度分散,且钙与镧之间有较强的协同作用。催化剂适宜的制备条件：钙与镧物质的量比为2∶1,焙烧温度为750 ℃,焙烧时间为3 h。在醇与油物质的量比为13∶1、催化剂质量占大豆油质量的4%、反应时间为4 h条件下,制备的氧化钙/三氧化二镧固体碱催化剂催化大豆油和甲醇进行的酯交换反应制备生物柴油的产率达到90%以上。     

Cu/TS-1催化苯甲醇选择性氧化制苯甲醛

以浸渍法制备了不同金属改性的TS-1分子筛催化剂M/TS-1,(M=Cu,Fe,Zn,Co,Cr,Mn,V,负载量为2%),用于催化苯甲醇选择性氧化制取苯甲醛。采用X射线衍射(XRD)、傅里叶红外光谱(FT-IR)以及扫描电子显微镜(SEM)对TS-1进行了表征。结果表明,TS-1分子筛在引入不同金属后,均保持了MFI的拓扑结构及其形貌特征。氮气吸附法(BET)以及电感耦合等离子体原子发射光谱(ICP-AES)分析表明,各金属物种均匀地分散在TS-1分子筛表面,并且没有堵塞TS-1分子筛的孔道结构。金属的引入能够提高TS-1分子筛在苯甲醇氧化制苯甲醛反应中的催化活性,其中Cu负载的TS-1分子筛在以叔丁基过氧化氢(TBHP)作氧化剂氧化苯甲醇的反应中显示出了优异的催化活性,在反应4 h,反应温度323 K的条件下,苯甲醛的选择性98.2%,苯甲醇的转化率25.2%。     

Cu/TS-1催化苯甲醇选择性氧化制苯甲醛

以浸渍法制备了不同金属改性的TS-1分子筛催化剂M/TS-1,(M=Cu,Fe,Zn,Co,Cr,Mn,V,负载量为2%),用于催化苯甲醇选择性氧化制取苯甲醛。采用X射线衍射(XRD)、傅里叶红外光谱(FT-IR)以及扫描电子显微镜(SEM)对TS-1进行了表征。结果表明,TS-1分子筛在引入不同金属后,均保持了MFI的拓扑结构及其形貌特征。氮气吸附法(BET)以及电感耦合等离子体原子发射光谱(ICP-AES)分析表明,各金属物种均匀地分散在TS-1分子筛表面,并且没有堵塞TS-1分子筛的孔道结构。金属的引入能够提高TS-1分子筛在苯甲醇氧化制苯甲醛反应中的催化活性,其中Cu负载的TS-1分子筛在以叔丁基过氧化氢(TBHP)作氧化剂氧化苯甲醇的反应中显示出了优异的催化活性,在反应4 h,反应温度323 K的条件下,苯甲醛的选择性98.2%,苯甲醇的转化率25.2%。     

苯甲醇液相氧化合成苯甲醛的连续流工艺

在液相条件下以苯甲醇为原料,次氯酸钠溶液为氧化剂,2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）为氧化催化剂,在连续流微通道反应器中液相氧化合成苯甲醛。考察了苯甲醇与次氯酸钠溶液的物质的量配比、催化剂用量、反应温度、溶剂以及停留时间对苯甲醛合成的影响,并进行了工艺优化。结果表明：当次氯酸钠与苯甲醇的物质的量比为1.25∶1、苯甲醇与TEMPO的物质的量比为1∶0.01、苯甲醇与DMF的体积比为1∶10、 pH=8、反应温度为0℃、停留时间为10min时,苯甲醛的收率可达95.1%。     

V/Mo-HMS催化苯甲醇氧化制苯甲醛

以偏钒酸铵、磷钼酸为活性组分,采用溶胶-凝胶法原位合成钒、钼改性HMS介孔材料（V/Mo-HMS）。通过X射线衍射光谱（XRD）、扫描电镜（SEM）、N2吸附-脱附（BET）、H2程序升温还原(H2-TPR)、X射线光电子能谱（XPS）及热分析（TG-DTA）等手段对合成的V/Mo-HMS进行表征。同时以30%双氧水为氧化剂,V/Mo-HMS为催化剂,催化苯甲醇氧化制苯甲醛,讨论了不同金属改性HMS对催化反应的影响。结果表明,与HMS比较,V/Mo-HMS的比表面积、孔容及平均孔径均降低;0.1mol苯甲醇用0.8 mol 30% H2O2氧化,乙酸乙酯为溶剂,催化剂用量0.07 g,在90℃下反应6h,苯甲醇的转化率可达68.16%,苯甲醛的选择性达到89.02%。催化剂可回收重复使用。     

Highly selective gas-phase oxidation of benzyl alcohol to benzaldehyde over silver-containing hexagonal mesoporous silica

Silver-containing hexagonal mesoporous silica (Ag-HMS) catalysts with different Si/Ag ratios were synthesized by one-pot hydrothermal method for gas-phase selective oxidation of benzyl alcohol to benzaldehyde. The samples were characterized by nitrogen adsorption, X-ray diffraction, scanning electron micrograph, transmission electron micrograph, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectra. It was found that the Ag-HMS catalysts with different Ag loadings (0.55-3.50 wt.%) and different Ag particle sizes (5-32 nm) showed a similar level of catalytic property because they possess a similar Ag surface area. The Ag-HMS catalyst with a Ag loading of 2.81 wt.% exhibited excellent catalytic properties at 583 K with a high benzyl alcohol conversion of near 100%, benzaldehyde selectivity of around 96.0%, and benzaldehyde yield of about 96.0%, superior to those of other M-HMS catalysts (M = Co, Ce, La, Cu, Sr, Cd, Ni, Mn, V, and Fe). The enhanced catalytic performance could be attributed to the presence of the Ag surface oxygen species generated via oxygen spillover process. The work would be helpful for the development of novel Ag catalysts for selective oxidation of benzyl alcohol to obtain high quality of benzaldehyde and understanding the catalytic mechanism.     

锰卟啉-醋酸钴复合催化体系对甲苯氧气氧化的催化作用

研究了在无溶剂体系中,对氯四苯基锰卟啉［T(p-Cl)PPMnCl］和醋酸钴［Co(OAc)2］复合催化下,空气氧化甲苯制苯甲醛、苯甲醇和苯甲酸的新工艺。实验发现,T(p-Cl)PPMnCl/Co(OAc)2为复合催化剂时比单独使用T(p-Cl)PPMnCl 或Co(OAc)2时有更高的甲苯转化率和苯甲醛、苯甲醇、苯甲酸的收率,表现出明显的复合催化作用。研究表明,反应温度、反应时间和催化剂比例对T(p-Cl)PPMnCl/Co(OAc)2的复合催化效果有影响。     

氮杂碳包铁负载钯催化苯甲醇无溶剂氧化

以氮杂碳包铁(Fe@NC)为载体、聚乙烯吡咯烷酮为稳定剂,通过液相还原H_2PdCl_4和后续焙烧法制备新型的磁可分离Pd/Fe@NC催化剂,并进行AAS、TEM、XRD和XPS表征,将制备的催化剂用于苯甲醇无溶剂需氧氧化反应,考察焙烧温度、反应温度、催化剂用量和碱性助剂对其催化性能的影响,研究催化剂的循环使用性能。结果表明,Pd负载质量分数为4.86%,Pd有效负载比例为97.2%;Pd颗粒在载体上分散均匀,平均粒径为5 nm;催化剂活性物种组成包括Pd~0和含量较低的络合Pd(Ⅱ)及PdO。在无溶剂、无碱性助剂、O_2分压101.325 kPa(O_2流量为20 m L·min~(-1))和低催化剂用量[n(Pd)∶n(苯甲醇)=1∶2 000]条件下,Pd/Fe@NC可高效催化苯甲醇的氧化反应,100℃反应24 h,苯甲醇转化率达86%,苯甲醛选择性为87%,反应过程中无任何有毒物质产生与排放。催化剂循环使用7次后,催化活性略有提高,催化过程中络合的Pd(Ⅱ)向Pd0的转化是其活性提高的主要原因。     

复合固体超强酸SO42-/Fe2O3/Al2O3/ZnO的制备及其催化性能的研究

利用共沉淀法由Fe(NO3)3、Al(NO3)3、Zn(Ac)2和H2SO4制备了SO42-/Fe2O3/Al2O3/ZnO催化剂,并用于催化合成苯甲醛丙二醇缩醛,研究了醛醇摩尔比、催化剂用量、反应时间等因素对产品收率的影响。结果表明,在n(苯甲醛)∶n(丙二醇)=1∶1.2,催化剂用量为反应物总质量的1%,反应时间50 min的最佳条件下,苯甲醛丙二醇缩醛的收率可达97.6%。     

Aerobic oxidation of alcohols catalyzed by gold nano-particles confined in the walls of mesoporous silica

Gold nano-particles confined in the walls of mesoporous silica (GMS) catalysts were successfully prepared by a novel and simple technique utilizing thioether functional groups in the walls of mesoporous silica to anchor HAuCl₄. Calcination of the materials removed organic moieties and reduced the gold salt to gold nano-particles. In this procedure, the thioether groups were introduced into the silica wall via a co-condensation of tetraethyl orthosilicate (TEOS) with 1,4-bis(triethoxysily)propane tetrasulfide. These gold containing mesoporous catalysts have unusually high surface area and pore volume. The catalysts were evaluated for the solvent free liquid phase oxidation of benzyl alcohol by molecular oxygen. High selectivity to benzaldehyde was obtained under the reaction conditions of 403 K, 15 atm and 5 h in an autoclave. The 1.5% GMS catalyst was also evaluated for oxidation of alcohols using toluene as solvent under flowing oxygen at atmospheric pressure at 353 K in a two-necked flask. Under these conditions the conversion of benzyl alcohol reached 100% after 2 h and it was demonstrated that the catalyst can be recycled three times without significant loss of activity.     

Aerobic oxidation of alcohols over Au/TiO2: An insight on the promotion effect of water on the catalytic activity of Au/TiO2

The unique and significant promotion effect of water has been evidenced by the selective oxidation of benzyl alcohol to benzaldehyde over Au/TiO₂ catalysts. Water has dual promotional functions in the reaction system: to help form unique microdroplets in a multiphase reaction system and to assist the oxygen adsorption and activation. The conversion of benzyl alcohol at a molar ratio of water to solvent (p-xylene) of 7 is 7 times higher than in the absence of water. The present work has highlighted the potential of Au/TiO₂ catalysts in aerobic oxidation of alcohols in the unique multiphase reaction system with water as promoting solvent.     

Gold catalysed selective oxidation of alcohols in supercritical carbon dioxide

The oxidation of benzyl alcohol to benzaldehyde over different supported gold catalysts in supercritical carbon dioxide has been investigated in a high-pressure batch reactor. Only molecular oxygen was used as oxidant and no base was needed. Different supports and preparation methods for the catalysts were tested and parameters like reaction temperature, pressure and molar ratios of the components were varied to study the catalytic behaviour. Gold colloids deposited on a titania support (1%Au/TiO₂) yielded a conversion of 16.0% after 3 h and a high selectivity to benzaldehyde of 99% under single-phase conditions. The reaction rate was significantly higher than in a corresponding “solvent-free” reaction without CO₂. Even higher rates were found when a CO₂-expanded phase was present. Monitoring of the oxidation in a high-pressure view cell via infrared transmission spectroscopy unravelled a slowdown of the reaction rate above 15% conversion. In addition, 1-octanol and geraniol were oxidised as well under similar conditions, yielding conversions of 4% and 10%, respectively, with selectivities towards octanal and geranial of 90% and 30%. Thus, the combined application of gold-based catalysts and supercritical CO₂ offers an interesting alternative to the known methods of alcohol oxidation.     

Solvent-free liquid phase oxidation of benzyl alcohol to benzaldehyde by molecular oxygen using non-noble transition metal containing hydrotalcite-like solid catalysts

Performance of Co–Al, Ni–Al, Cu–Al, Zn–Cu–Al, Mg–Fe, Co–Fe, Ni–Fe, Mn–Cr, Co–Cr, Ni–Cr, Zn–Cr and Cu–Cr hydrotalcite-like solid catalysts has been evaluated for the liquid phase oxidation of benzyl alcohol to benzaldehyde using molecular oxygen as an oxidizing agent in the absence of any solvent. The Mn and Cu containing hydrotalcite-like solids show good catalytic activity in the oxidation and hence these are promising catalysts for the solvent-free oxidation reaction.     

Hydrogenation of Benzaldehyde over Palladium Intercalated Bentonite Catalysts: Kinetic Studies

Bentonite, a 2:1 type swellable phyllosilicate clay mineral having exchangeable inorganic cations in the interlamellar space to nullify their charge deficiency was used to generate palladium nanoparticles. It was found that 1% w/w palladium nanoparticles were generated in the interlamellar space using adsorption excess technique. The synthesized catalysts were characterized by using XRD, TEM, BET surface area analysis, and AAS. The modified clay catalysts were tested for their catalytic activity towards the hydrogenation of benzaldehyde to benzyl alcohol in liquid phase using a high-pressure reactor at various temperatures and pressures. High selectivity (100%) towards the desired product of benzyl alcohol was achieved with conversion over 80% in all cases. These results showed different hydrogen dependency for the reaction at various temperatures. The kinetics of the reaction was studied using Langmuir Hinshelwood single site model. The rate constant was determined using pseudo first-order kinetics and activation energy for benzaldehyde hydrogenation was calculated at various temperatures using Arrhenius equation and was found to decrease with increase in temperature.