赤泥磷酸浸出液中稀土的萃取行为研究

赤泥是铝土矿生产氧化铝过程中产生的固体残渣，含有铁、硅、铝、钛及稀土等多种有价组分。在已预先分离赤泥中大部分铁、硅、铝、钛的前提下，采取溶剂萃取的方式对赤泥磷酸浸出液中的稀土作进一步分离与纯化，研究了在中性磷型萃取剂TBP、酸性磷型萃取剂P204和P507分别作用下，稀土La、Ce、Sc、Y以及主要杂质组分Al、Fe、Ti、Ca的萃取行为，结果表明：TBP对稀土的萃取效果较差，P507对稀土Sc、Y及杂质Fe、Ti的萃取能力较强，P204萃取稀土的能力优于P507;采用质量分数2%P204作为萃取剂，在溶液pH为1.5、相比为1∶3的条件下，磷酸浸出液中Sc、Y的萃取率分别为90%、99%,La、Ce及杂质Fe、Al、Ti、Ca萃取率均低于5%;将P204质量分数升至20%,La、Ce萃取率可分别达到85%、95%。因此可通过采用P204分步萃取的方式有效分离磷酸浸出液中的稀土。     

Mn／Ce／La复合催化剂湿式氧化处理苯酚废水的研究

为了研制高效稳定的新型催化剂,采用共沉淀方法制备了Mn／Ce/La复合催化剂,用于催化湿式氧化处理苯酚模拟废水,考察了催化剂制备条件和催化反应条件对催化剂性能的影响。以NaOH为沉淀剂,将混合盐沉淀物常温下老化0．5h,378K干燥12h,873K焙烧1h,研磨至粒径为75μm．制得Mn／Ce,／La复合催化剂。催化剂最佳配比为n（Mn）：n（Ce／La）：5：5（n（Ce）：n（La）=（2：1）。     

镧和铈改性CuNi／Al2O3催化剂

采用浸渍法制备了稀土镧和铈改性的CuNi／Al2O3催化剂,研究了稀土负载量对催化剂活性和选择性的影响,并研究了催化剂的还原性能。结果表明：La和Ce的存在均降低了活性相CuO和NiO的还原温度,使改性催化剂具有更高的催化活性,但催化剂上乙烯的选择性则是Ce改性催化剂高于La改性催化剂,NCeO2含量为l％时,CeCuNi／Al2O3催化剂上乙炔转化率达到98％,乙烯选择性和收率则分别达到84％和82．3％,比未改性的CuNi／Al2O3催化剂上乙烯收率高16．4％,显示出CeO2改性CuNi／Al2O3催化剂的优异性能。     

非热等离子体协同Mn-Ce/La/γ-Al2O3催化剂去除甲苯

采用自制线管式介质阻挡放电反应器,针对非热等离子体协同Mn-Ce/La/γ-Al₂O₃催化剂对低浓度甲苯的去除开展研究。研究中制备了Mn/γ-Al₂O₃、Mn-Ce/γ-Al₂O₃、Mn-La/γ-Al₂O₃催化剂,从甲苯去除率、产物O₃生成、CO_x选择性及其他副产物生成情况考察比较了空管放电、协同催化剂放电时催化降解甲苯性能,并对催化剂进行了BET、SEM、H₂-TPR和ICP-OES表征研究。结果表明：稀土助剂的加入有助于提高甲苯去除率及降低程度,且La催化性能优于Ce_.,当外加电压22 kV、气量6 L·min^-1、甲苯初始浓度600 mg·m^-3时,Mn-La/γ-Al₂O₃催化剂对甲苯去除率达到72.74%。H₂-TPR结果表明,稀土助剂的加入提高了催化剂低温活性及储氧能力,添加La的效果优于Ce。催化剂有助于抑制副产物O₃生成,提高CO₂和CO_x选择性。     

La3+掺杂TiO2光催化性能研究

采用溶胶-凝胶法制备了La^3＋／TiO2光催化剂,研究了该催化剂对亚甲基蓝的光催化降解效果。结果表明,La^3＋掺杂量（摩尔分数）2．8％、催化剂用量1．2g／L、体系pH值为11时,12mg／L亚甲基蓝溶液经2h光催化降解,其降解率可达99．1％。与纯TiO2相比,La^3＋/TiO2光催化剂显示出良好的光催化活性。     

稀土含量（La）对USY分子筛性能及其焦炭选择性的影响

采用XRD、固定床微反装置、快速精密定炭仪研究了用高温水蒸气法及稀土LaCl3改性NaY分子筛后分子筛的稳定性、活性及其焦炭选择性。结果表明,随着USY分子筛La含量的增加,其晶胞常数增大,活性增加,结晶度减小,老化后的533峰保留率降低,结晶度的降低并不是真正意义上的分子筛减少,而是稀土干扰导致的。综合比较稀土含量和晶胞的作用,可知晶胞大小可能是影响稳定性的最主要因素,而后才是稀土的影响。La含量增加,积炭含量增加,其焦炭选择性变差。     

杯[8]芳烃萃取稀土金属离子的研究

合成了对叔丁基杯[8]芳烃,研究了其对稀土金属钕、铕、镨离子(Nd^3 、Eu^3 、Pr^3 )在溶液中的萃取。测定了在25℃,离子强度I=0．1g／mol时Nd^3 、Eu^3 、Pr^3 的萃取平衡常数。探讨了杯[8]芳烃萃取分离这3种稀土金属离子的条件、萃取反应机理及其规律性。     

高纯氧化铥的分离制备研究

用ＣＬ－Ｐ５０７－ＨＣｌ体系柱色层法分离原料氧化铥中铒、镱等稀土和非稀土杂质。讨论了树脂粒度、温度、淋洗剂浓度１负载量、进样比等条件对铥、镱 分离的影响,观没蛭铥、镱之间存在萃取抑制现象。选择合适分离条件以９９．９％氧化铥 为原料制备出９９．９９５％的高纯氧化铥产品,其主要稀土杂质铒,镱 均小于５μｇ／ｇ,非稀土杂质铁小于２μｇ／ｇ,钙小于５μｇ／ｇ。     

助剂对催化剂CuO／Al2O3／CC活性的影响

以改性后的堇青石为惰性载体，采用浸渍法制备了一系列Cu系催化剂，活性考察表明，Cu—Mn—Ni—Ce—O／Al2O3／CC催化剂低温活性比较高，反应温度在150℃时转化率达50．46％，300℃达到100％。BET、XPS和TPR测试表明，助剂Mn、Ni和Ce的添加，增大了Cu系催化剂比表面积和平均孔径，使催化剂更易被还原，催化剂表面的元素以Cu^2＋、Mn^4＋、Mn^3＋、Ni^2＋和Ce^4＋价态的氧化态物种存在。     

以D2EHPA-TOPO为载体的乳化液膜体系萃取磷酸中La（Ⅲ）的工艺及传质机理研究

通过以二（2-乙基己基）磷酸酯／氧化三辛基膦（D2EHPA／TOPO）为流动载体,磺化聚丁二烯（LYF）为表面活性剂,液体石蜡为膜增溶剂,煤油为稀释剂,盐酸为内水相的W／O型乳液,与含La（Ⅲ）的磷酸的外水相进行萃取的过程,制备了W／O／W的双重乳化液膜体系,用单因素法考察了载体浓度,表面活性剂浓度,内相酸度,水乳比等对液膜提取率的影响,确定了最佳工艺条件,迁移率达94．21％以上。并以单浓度递变斜率法研究了载体浓度,表面活性剂浓度,磷酸浓度,H2PO4^-浓度,水相平衡H^＋浓度对分配比的影响,推导出了该乳化液膜的传质机理所经历的步骤。传质机理中包括萃取-反萃表达式,和协萃物组成La（H2PO4）L2（HL）2·（H3PO4）·2TOPO。     

Sintering mechanism and properties of ZnVMnNbO varistor ceramic and their evolutions by Ce–La doping

This paper studies the sintering mechanism and property of ZnO–V₂O₅–MnCO₃–Nb₂O₅ (ZnVMnNbO) varistor ceramic and their evolution by Ce–La dopant. The XRD, SEM, EBSD and TEM results show MnZn₂Nb₂O₈ has a similar effect as ZnV₂O₄ and Zn₃(VO₄)₂ on contributing to the formation of Vanadium (V)-rich liquid phase and promoting the sintering of ZnVMnNbO ceramic. Oppositely, ZnMn₂O₄ particle phase can only postpone sintering by pinning the growth of ZnO grains. Adding Ce–La dopant leads to forming Ce(La)VO₄ intergranular particle phase that further hinders the sintering of the ceramic. This conclusion agrees with the result of the following kinetics study that shows the grain-growth exponent and apparent activation energy of ZnVMnNbO ceramic increasing from 2.39 and 186 KJ mol-1 to 2.95 and 263 KJ mol-1 with the addition of Ce–La dopant. Meanwhile, the electrical properties of the Ce–La doped ZnVMnNbO varistor ceramics are generally better than its Rare Earth (RE)-free counterparts. Sintering at 875 °C for 3 h can increase the nonlinear coefficient of Ce–La doped ZnVMnNbO varistor ceramic to its highest value of 48.4, therefore, is proposed as the optimum fabricating procedure.     

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。     

镧铈稀土PVC热稳定剂的制备及性能研究

以包头稀土矿初步分离得到的镧铈混合稀土、氰尿酸、硝酸、氢氧化钠为原料合成了聚氯乙烯(PVC)热稳定剂——氰尿酸镧铈,通过刚果红试纸法研究了氰尿酸镧铈对PVC的热稳定作用及变色情况的影响,并与氰尿酸镧、硬脂酸镧、硬脂酸钙、硬脂酸锌等热稳定剂进行了比较。结果表明:氰尿酸镧铈具有良好的热稳定作用,其热稳定效果与硬脂酸镧相近,略逊于氰尿酸镧,但完全可以作为热稳定剂单独使用,从而省掉分离镧铈混合稀土而产生的额外费用。     

Synthesis of flower-like La or Pr-doped mesoporous ceria microspheres and their catalytic activities for methane combustion

La or Pr-doped flower-like mesoporous ceria microspheres were prepared by a unique calcination of La or Pr-doped Ce(OH)CO₃ microspheres hydrothermally synthesized with the aid of glucose and acrylic acid. Prepared flower-like ceria-based materials have a novel hierarchical architecture with mesoporous structure and high surface area, which can obviously facilitate the catalytic combustion of methane, compared with general La or Pr-doped ceria. The presence of La or Pr can promote the production of oxygen vacancies and improve oxygen mobility, which result in enhancing the oxygen-storage capacity of the flower-like ceria and its catalytic performance for the methane combustion.     

Interfacial reaction between La–Ce alloy and submerged entry nozzle controlled by external electric field

In order to restrain the clogging in submerged entry nozzle (SEN) during the casting of rare earth steel, La–Ce alloy is explored in this work. Effects of external electric field on reaction behavior of La–Ce alloy with SEN are investigated. Results show that chemical mechanisms between La–Ce alloy and SEN during the reaction cannot be altered by electric field due to strong chemical reaction force of rare earth elements against SEN, but the speed of chemical reaction can be controlled by electric field, resulting in significant changes in reactions. By the application of positive electric field, stable and dense interface reaction layer can be formed on the surface of SEN. Specifically, newly formed protective layer can limit the formation of clogging at initial stage to continue till the end of the reaction. Proposed novel approach of external positive electric field can be expected to solve the clogging of SEN during rare earth steel casting process.     

And Yet It Moves: Oxidation of the Nuclear Autoantigen La/SS-B Is the Driving Force for Nucleo-Cytoplasmic Shuttling

Decades ago, we and many other groups showed a nucleo-cytoplasmic translocation of La protein in cultured cells. This shuttling of La protein was seen after UV irradiation, virus infections, hydrogen peroxide exposure and the Fenton reaction based on iron or copper ions. All of these conditions are somehow related to oxidative stress. Unfortunately, these harsh conditions could also cause an artificial release of La protein. Even until today, the shuttling and the cytoplasmic function of La/SS-B is controversially discussed. Moreover, the driving mechanism for the shuttling of La protein remains unclear. Recently, we showed that La protein undergoes redox-dependent conformational changes. Moreover, we developed anti-La monoclonal antibodies (anti-La mAbs), which are specific for either the reduced form of La protein or the oxidized form. Using these tools, here we show that redox-dependent conformational changes are the driving force for the shuttling of La protein. Moreover, we show that translocation of La protein to the cytoplasm can be triggered in a ligand/receptor-dependent manner under physiological conditions. We show that ligands of toll-like receptors lead to a redox-dependent shuttling of La protein. The shuttling of La protein depends on the redox status of the respective cell type. Endothelial cells are usually resistant to the shuttling of La protein, while dendritic cells are highly sensitive. However, the deprivation of intracellular reducing agents in endothelial cells makes endothelial cells sensitive to a redox-dependent shuttling of La protein.     

La/Zn/HZSM-5催化剂上的甲醇芳构化研究

Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.     

溶胶-凝胶微波加热合成Ca_(2.7)La_(0.3)Co_4O_9前驱粉

以硝酸钙、硝酸钴、硝酸镧和柠檬酸等为原料,用溶胶-凝胶法制备出凝胶,在100℃下烘干,然后用微波炉加热,合成了Ca2.7La0.3Co4O9前驱粉体。讨论了微波合成参数对粉体晶相和晶粒度的影响。用X射线衍射仪(XRD)、扫描电子显微镜(SEM)对制备的粉体进行了测试。结果表明,溶胶-凝胶结合微波加热法可以在较短的时间内制得Ca2.7La0.3Co4O9粉体,且晶形发育比常规加热更完善。微波高火加热20min,可得到纯相的Ca2.7La0.3Co4O9前驱粉。     

Au/La2O3/TiO2催化甲醇水蒸汽重整制氢

用沉积-沉淀法制备了Au/La2O3/TiO2催化剂,考察了制备条件和反应条件对催化剂活性的影响,并利用X射线衍射(XRD)、透射电子显微镜(TEM)等测试手段对催化剂进行了表征. 结果表明La2O3的加入可使催化剂催化甲醇水重整的催化活性明显提高,且明显降低产物气体中CO和CH4的含量,使氢气选择性明显增加. 当nH2O/nCH3OH=1.0、液体进料空速WHSV=3.42 h-1、反应温度为275℃时,Au/La2O3/TiO2催化剂催化甲醇水蒸汽重整制氢反应的效果最佳.     

La／B共掺杂Ti02光催化降解苋菜红的研究

采用溶胶-凝胶法制备La/B共掺杂Ti O2催化剂和纯TiO2催化剂。以苋菜红溶液为降解目标物,研究了La/B共掺杂TiO2为催化剂的紫外光催化反应。重点考察了La/B共掺TiO2催化剂的掺杂比、催化剂的煅烧温度、光照时间、催化剂的添加量、溶液初始浓度、溶液p H值对降解率的影响。实验结果表明：单纯只靠紫外光光照或催化剂并不能快速、有效地降解苋菜红溶液。在La和B掺杂比为1：2、催化剂的煅烧温度为600℃、催化剂用量为3.0g/L、溶液p H值为5.5、溶液初始浓度为10mg/L的苋菜红溶液200m L,紫外光光照60min的条件下,La/B共掺杂的TiO2催化剂和纯TiO2催化剂光催化脱色率分别可达99.60%、86.45%,TOC的去除率为60.06%。