SO42-/TiO2-La2O3催化剂催化合成苹果酯-B

制备了稀土改性固体超强酸SO42-/TiO2-La2O3催化剂。以SO42-/TiO2-La2O3为多相催化剂,对以乙酰乙酸乙酯和1,2-丙二醇为原料合成苹果酯-B的反应条件进行了研究。实验表明:固体超强酸SO42-/TiO2-La2O3是合成苹果酯-B的良好催化剂,最佳反应条件为:n(乙酰乙酸乙酯)∶n(1,2-丙二醇)=1∶1.5,催化剂用量为反应物料总质量的1.5%,环己烷为带水剂,反应时间1.5h,反应温度85℃～110℃。在上述条件下,苹果酯-B的收率可达88.6%。     

稀土改性固体超强酸SO42-/TiO2-MoO3-La2O3催化合成环己酮1,2-丙二醇缩酮

报道了以稀土改性固体超强酸SO42-/TiO2-MoO3-La2O3为多相催化剂,通过环己酮和1,2-丙二醇反应合成了环己酮1,2-丙二醇缩酮,探讨了SO42-/TiO2-MoO3-La2O3对缩酮反应的催化活性,采用正交试验法系统地研究了酮醇量比,催化剂用量,反应时间诸因素对产品收率的影响。实验表明,稀土改性固体超强酸SO42-/TiO2-MoO3-La2O3是合成环己酮1,2-丙二醇缩酮的良好催化剂,在n(环己酮)∶n(1,2-丙二醇)=1∶1.6,催化剂用量为反应物料总质量的0.4%,环己烷为带水剂,反应时间1.0 h的优化条件下,环己酮1,2-丙二醇缩酮的收率可达88.8%。     

SO2-4/TiO2-WO3催化合成环己酮1,2-丙二醇缩酮

介绍了以固体超强酸SO42-/TiO2-WO3为多相催化剂,通过环己酮和1,2-丙二醇反应合成了环己酮1,2-丙二醇缩酮,探讨了SO24-/TiO2-WO3对缩酮反应的催化活性,较系统地研究了酮醇量比,催化剂用量,反应时间诸因素对产品收率的影响.实验表明:SO24-/TiO2-WO3是合成环己酮1,2-丙二醇缩酮的良好催化剂,在n(环己酮):n(1,2-丙二醇)=1:1.5,催化剂用量为反应物料总质量的1.25%,环己烷为带水剂,反应时间1.5 h的优化条件下,环己酮1,2-丙二醇缩酮的收率可达88.5%.     

SO42-/TiO2-La2O3催化剂催化合成丁醛1,2-丙二醇缩醛

报道了以稀土改性固体超强酸SO42-/TiO2-La2O3为多相催化剂,通过丁醛和1,2-丙二醇为原料合成丁醛1,2-丙二醇缩醛,探讨了SO42-/TiO2-La2O3催化剂对缩醛反应的催化活性,较系统地研究了原料量比,催化剂用量,反应时间诸因素对产品收率的影响.实验表明在n(丁醛)∶n(1,2-丙二醇)=1∶1.5 ,催化剂用量为反应物料总质量的0.50%,环己烷为带水剂,反应时间1.0 h的优化条件下,丁醛1,2-丙二醇缩醛的收率可达95.8%.     

含铈固体超强酸SO42-/SnO2-CeO2-kaolin催化合成异丁酸异丁酯

以质量比为1:9:20的硝酸铈铵、高岭土和SnCl4·5H2O制备了含铈固体超强酸催化剂SO42- -/SnO2-CeO2-kaolin,制备条件为促进剂H2SO4浓度2.0mol/L,浸渍12h,350℃焙烧3h,并采用Hammett指示剂法和XRD对其进行了酸强度和表面性能表征.适宜反应条件是催化剂用量为反应物总质量的2.5%,醇酸摩尔比1.4、反应时间100min,甲苯10mL,酯收率94.5%,重复使用6次酯收率仍高于80%.     

稀土固体超强酸Ce4+-SO42-/ZrO2催化剂的制备及性能研究

将固体超强酸SO42-/ZrO2负载稀土铈,制备了新型催化剂Ce4+-SO42-/ZrO2,用于催化合成溴代正辛烷。考察了硝酸铈的质量百分浓度、焙烧温度、焙烧时间等因素对其催化性能的影响;并采用IR、XRD和Hammett指示剂法对其性能进行了研究。     

稀土掺杂固体超强酸SO2-4/TiO2催化合成二芳基乙烷的研究

研究了以稀土元素Sm、Nd、Y对固体超强酸SO2- 4/TiO2进行改性,并用于催化合成二芳基乙烷,考察了影响反应的因素.结果表明,稀土掺杂固体超强酸SO2-4/TiO2/REn+具有催化性能高、性能稳定且连续催化活性基本保持不变的优点.最佳实验条件为:苯乙烯与二甲苯之比为1∶7.5,催化剂用量为1%(总投料质量分数),反应时间为3小时,反应温度为回流温度,产率可达96.7%.     

新型SO2-4/TiO2-MoO3催化剂的制备方法及其应用实例--催化合成异丁醛丙二醇缩醛新工艺

详实地阐述了新型固体超强酸SO2-4/TiO2-MoO3催化剂的制备方法及其应用实例———催化合成异丁醛1,2-丙二醇缩醛新工艺。合成实践表明,SO2-4/TiO2-MoO3是合成缩醛(酮)的优良环保型催化剂,具有显著的技术、经济效益。     

固体超强酸S_2O_8~(2-)/TiO_2-WO_3的制备及其催化性能研究

用溶胶-凝胶法制备了固体超强酸S2O82-/TiO2-WO3,并对其进行了XRD与IR表征,用乙酸乙酯合成模型反应考察了其催化性能,系统研究了WO3的含量、焙烧温度等制备条件对S2O82-/TiO2-WO3性能的影响。实验表明:在(NH4)10W12O41.xH2O质量分数为5.0%、焙烧温度为500℃条件下通过溶胶-凝胶法制备的固体超强酸S2O82-/TiO2-WO3,其载体为微细且晶格不太完整的锐钛矿型TiO2,比表面积较大,具有比浸渍法制备的SO42-/TiO2更高的硫含量和更强酸性,并具有较高的催化酯化活性和稳定性,在反应条件为:醇酸摩尔比1.48∶1、催化剂用量为冰醋酸的6.0%、反应时间2.0h,乙酸转化率可达74.1%(不加分水器)。催化剂在无需任何再生的条件下重复使用,活性下降趋势平缓,显示良好的稳定性。     

SO2-4/TiO2-WO3催化合成丁醛1,2-丙二醇缩醛

以固体超强酸SO2-4/TiO2-WO3为催化剂,对以丁醛和1,2-丙二醇为原料合成丁醛1,2-丙二醇缩醛的反应条件进行了研究.实验表明SO2-4/TiO2-WO3是合成丁醛1,2-丙二醇缩醛的良好催化剂,研究了醛醇摩尔比、催化剂用量、反应时间诸因素对收率的影响.最佳反应条件为n(丁醛)/n(1,2-丙二醇)=1/1.4,催化剂用量为反应物料总质量的0.5%,环己烷为带水剂,反应时间50 min.上述条件下,丁醛1,2-丙二醇缩醛的收率可达84.6%.     

铕掺杂固载超强酸催化合成三醋酸甘油酯的研究

分别以粘土制成的陶瓷球、分子筛为载体,四氯化钛和三氯化铕为原料,采用液相沉积法制备了掺杂铕的T iO2/SO42-/陶瓷球固载超强酸(ETT)和掺杂铕的T iO2/SO42-/分子筛固载超强酸(ETS)。通过正交试验优选了催化剂制备条件,并以甘油与醋酸的酯化反应考察了催化剂的催化性能。实验结果表明,T iO2等化合物在载体上的沉积速度是影响催化剂活性的关键因素,且载体不同时会影响到催化剂对酯化反应的催化活性。在适宜的条件下,即原料配比n甘油∶n乙酸∶n乙酸酐为1∶4∶0.2,催化剂(ETT)用量2.5g(为总投料量的2.6%),反应时间7h时,三醋酸甘油酯的收率可达到98.3%。     

Effects of MO_x(M=Mn,Cu,Sb,La)on V-Mo-Ce/Ti selective catalytic reduction catalysts

A series of MO_x-V_2O_5-MoO_3-CeO_2/TiO_2(M=Mn,Cu,Sb,and La) catalysts were prepared via an impregnation method.The physico-chemical properties of the catalysts were characterized and their NH_3-SCR of NO performance was compared.The Mn-loaded catalyst(Mn5V1Mo3Ce7/Ti) exhibits a large number of acid sites of varying strength,and together with good reducibility of the catalyst,contributes to the optimal SCR performance.The sulphate species formed in the presence of SO_2 significantly enhance the H_2O and SO_2 tolerance of Mn5V1Mo3Ce7/Ti.The Cu-loaded catalyst(Cu5V1Mo3Ce7/Ti)demonstrates potential in flue gas applications in the absence of SO_2 at low temperatures because of the excellent redox ability observed and the high degree of weak acid sites.The Sb and La loaded catalysts(Sb5V1Mo3Ce7/Ti and La5V1Mo3Ce7/Ti),especially La5V1Mo3 Ce7/Ti,exhibit the largest number of acid sites and the lowest reducibility,and therefore,may be suitable for use in high temperature denitrification applications.     

新型稀土固体超强酸催化剂的制备及乳酸丁酯的合成

制备了一系列稀土固体超强酸催化剂,以乙酸丁酯为探针反应,考察了催化剂最佳制备条件;以乳酸和丁醇为原料,以S2O82-/ZrO2-SiO2-Sm2O3(BR-3%-0.75-450)为催化剂合成乳酸丁酯,研究了对酯化反应的影响因素、催化剂稳定性。实验结果表明,该催化剂活性和稳定性均优于未改性的SO42-/ZrO2-SiO2。     

New insights into MnCe(Ba)O_x/TiO_2 composite oxide catalyst:Barium additive accelerated ammonia conversion

MnCeO_x/TiO_2 has been widely used in selective catalytic reduction(SCR) of NO_x at low temperature.However,it is often poisoned in the presence of water vapor and sulfur dioxide.In this work,the promotion mechanism of Ba modification was investigated.Results show that the doped BaO reacts with CeO_2 and forms BaCeO_3.This unique perovskite structure of BaCeO_3 significantly enhances NO oxidation and NH_3 activation of MnCeO_x/TiO_2 catalyst so that the NO conversion and the resistances to SO_2 improve.It is found that Ba species obviously promotes the NO adsorption ability and improve the redox properties of MnCeO_x/TiO_2 catalyst.While the acid properties of the catalyst are inhibited by Ba modification and among which Lewis acid sites are dominant for both MnCeO_x/TiO_2 and MnCe(Ba)O_x/TiO_2 catalysts.Furthermore,in situ DRIFT experiments reveal that the NO reduction upon MnCeO_x/TiO_2 and MnCe(Ba)O_x/TiO_2 catalysts follows both E-R and L-H mechanisms,in which L-H is preferred.Ba species enhances the formation of active nitrate species,which accelerates the NO reduction through L-H mechanism.It is interesting that although Ba species weakens the NH_3 adsorption,it induces the ammonia conversion to coordination ammonia,which in turn accelerates the catalytic reaction.     

纳米TiO2/SnO2粉体的溶胶-凝胶法制备研究

以有机、无机盐为原料，通过加入稳定剂、催化剂，采用溶胶一凝胶法制备了TiO2、SnO2和TiO2／SnO2纳米微粒，采用XRD、SEM和XPS等技术对粒子的结构和组成进行分析，研究结果表明：TiO2／SnO2粒子主要由锐钛矿型TiO2和金红石型SnO2组成，与纯TiO2、SnO2相比，TiO2／SnO2微粒的粒度小、分布均匀、不团聚。     

硅胶担载硫酸铈催化合成丁二酸二乙酯

首次以硅胶担载硫酸铈(Ce(SO4)2/SiO2)为催化剂,合成了丁二酸二乙酯,该催化剂活性组分用量少,催化活性高,易分离,不腐蚀设备,无废酸排放,是一种环境友好催化剂。考察了影响反应的条件,获得优化试验条件:Ce(SO4)2担载量15%,丁二酸0.1mol,无水乙醇0.7mol,催化剂1.0g,反应时间2h,酯化率达91.5%。     

Anion structural effects on interaction of rare earth element ions with Dowex 50W X8 cation exchange resin

The effect of the anion in the original rare earth element(REE) solution on the reversible ion exchange of Ce nitrate and Ce sulfate with the Dowex 50 W X8 was investigated using attenuated total reflection infrared(ATR-IR) spectroscopy, continuous flow reactor studies coupled with inductively coupled plasma mass spectroscopy(ICP-MS), and density functional theory(DFT). The simulated IR spectrum at the DFT B3 LYP/6-31 G(d) level was compared to the experimental results to characterize the IR spectrum, molecular interactions, and bonding of the ion exchanged species. The continuous liquid flow reactor studies show a capacity of 0.72 mmol/g sorbent for the Ce nitrateand 0.96 mmol/g sorbent for the Ce sulfate with the Dowex 50 W X8. The flow reactor studies reveal the type of solute anion(SO_4~((2-)) or NO_3~((-))) associated with the REE during cation exchange significantly affects the sorption capacity of the Dowex 50 W X8 ion exchange resin. The calculated REE binding energy(BE) and the DFT optimized structures suggest that the differences in sorption capacity is the result of the formation of different types of partially ionexchanged Ce_2~((3+))2 SO_4~((2-)) and Ce~((3+)) 3 NO_3~((-)). These results suggest that the solute anion affects the equilibrium constants of the Dowex resin by the formation of a charged layer capable of retaining the counterion. Modifying the sulfonic acid site(H+) in the Dowex 50 W X8 with the NH_4~+ counterion does not affect the sorption capacity and retention times of the Ce nitrate and Ce sulfate species. These results suggest that the counterions and co-ions having a finite size, may limit access to the Dowex sulfonate active site where the type of REE cation as a nitrate or sulfate in solution may significantly modify the sorption capacity of the ion exchange resin. Similar results are obtained during sorption with nitrates and sulfates of Sm and Yb.     

Synthesis and Photocatalytic Activity of TiO2/V2O5 Composite Catalyst Doped with Rare Earth Ions

TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange （MO） in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4＋ present the best activity to MO.     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.     

硫酸铵-四丁基溴化铵-碘化钾体系浮选分离铂(Ⅳ)的研究

在0.1 g/mL硫酸铵、5.0×10-4mol/L四丁基溴化铵(TBAB)和3.0×10-3mol/L碘化钾存在下,铂(Ⅳ)形成的水不溶性的缔合物[PtI6][TBAB]2在水相表面浮选析出,而在此相同条件下,Zn(Ⅱ)、Cr(Ⅲ)、Mo(Ⅵ)、Fe(Ⅱ)、V(、Sn(Ⅳ)、Mn(Ⅱ)、Ni(Ⅱ)、Ga(Ⅲ)、Rh(Ⅲ)、Co(Ⅱ)、W(Ⅵ)、Al(Ⅲ)、Ce(Ⅲ)和Zr(Ⅳ)15种离子均不形成不溶性沉淀物。据此可达到铂(Ⅳ)与上述共存离子之间的定量分离。本法用于Ni-Pt/Al2O3催化剂中铂的分离和测定,平均回收率为97.1%,相对标准偏差(RSD)为2.2%(n=5)。