苯甲酸铒的热分解反应机理研究

由水热法合成了苯甲酸铒配合物,用元素分析、ＩＲ表征了该配合物。它为层状结构。用ＴＧ、ＤＴＡ、ＩＲ研究了它的热分解机理。在氮气气氛下,热分解分两步进行：第一步分解生成二碳酸一氧盐和有机化合物;第二步二碳酸一氧盐进一步分解生成氧化物和二氧化碳。第一步中生成的有机化合物主要成分为二苯甲酮、９,１０－蒽醌和１,３－二苯基异苯并呋喃等。     

Decomposition Reaction of Mixed Rare Earth Concentrate and Roasted with CaO and NaCl

The reaction of the mixed rare earth concentrate including monazite ( REPO4 ) and bastnaesite ( REFCO3 )decomposed by CaO and NaCl additives at the temperature range from 100 to 1000 ℃ was studied by means of XRD and TG-DTA.The results show that when CaO and NaCl are not added, only REFCO3 can be decomposed at the temperature of 377 ～ 450 ℃.The decomposition products include REOF, RE2O3 and CeO2.However, REFCO3 can not be decomposed.When CaO is added, the decomposition reactions occur at the temperature range from 660 to 750 ℃.CaO has three decomposition functions: ( 1 ) REPO4 can be decomposed by CaO and the decomposition products include RE2O3 and Ca3 (PO4)2; (2) CaO can decompose REOF, and the decomposition products are RE2O3 and CaF2; (3)CaO can decompose REPO4 with CaF2, and the decomposition products are RE2 O3, Ca5 F( PO4 )3.The decomposition ratio of the mixed rare earth concentrate increased obviously, when CaO and NaC1 were added.NaC1 can supply the liquid for the reaction, improve the mass transfer process and accelerate the reaction.At the same time, NaC1 participated in the reaction that REPO4 was decomposed by CaO.     

Preparation，Structural Characterization and Thermal Decomposition Mechanism of Rare Earth Salts of 3－Nitro－1，2，4－Triazol－5－One

Ｐｒｅｐａｒａｔｉｏｎ，ＳｔｒｕｃｔｕｒａｌＣｈａｒａｃｔｅｒｉｚａｔｉｏｎａｎｄＴｈｅｒｍａｌＤｅｃｏｍｐｏｓｉｔｉｏｎＭｅｃｈａｎｉｓｍｏｆＲａｒｅＥａｒｔｈＳａｌｔｓｏｆ３－Ｎｉｔｒｏ－１，２，４－Ｔｒｉａｚｏｌ－５－ＯｎｅＺｈａｎｇＴｏｎｇｌ...     

Synthesis, Characterization and Vulcanizing Properties of Rare Earth Complexes with 2-Mercaptobenthiazole

2 ｍｅｒｃａｐｔｏｂｅｎｚｏｔｈｉａｚｏｌｅｗａｓｆｉｒｓｔｒｅｐｏｒｔｅｄｂｙＨｏｆｍａｎｎ[1 ] ｉｎ 1 887.Ｉｔｈａｓｂｅｅｎｕｓｅｄａｓａｎａｃｃｅｌｅｒａｔｏｒｉｎｔｈｅｖｕｌｃａｎｉｚａｔｉｏｎｏｆｒｕｂｂｅｒｆｏｒｍａｎｙｙｅａｒｓ .Ｔｏｄａｙｉｔｉｓｓｔｉｌｌｂｅｉｎｇｕｓｅｄａｓａｍａｉｎａｃｉｄｉｃａｃｃｅｌｅｒａｔｏｒｉｎｒｕｂｂｅｒｉｎｄｕｓｔｒｙ .Ｂｕｔｉｔｈａｓｄｉｓａｄｖａｎｔａｇｅｓｏｆｖｕｌｃａｎｉｚａｔｉｏｎｒｅｖｅｒｓｉｏｎａｎｄｅａｓｙｓｃｏｒｃｈ[2 ] ｗｈｅ…     

Synthesis, Characterization and Luminescent Properties of Complexes of Rare Earth Nitrates with 2,2′:4′,4″:2″,2-Quaterpyridine

The rare earth nitrate complexes with 2,2′:4′,4″:2″,2-quaterpyridine (L) were prepared in ethylacetate. These new complexes with the general formula [RE(NO3)3L]*H2O (RE = La, Pr, Eu, Tb, Er, Y) were characterized by elemental analysis, IR spectra, thermal analysis and molar conductance measurements. The luminescence properties of these complexes were also studied.     

Synthesis and Structures of A Series of Novel Rare Earth Transition Metal Sulfates

Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae ： REM （OH） 3 （SO4） and RE2M （OH） 3 （SO4） 2F （H2O） with RE = Gd, Tb, Dy ; M = Ni, Cu. Three different crystal structure types were found for the formula REM （OH） 3 （SO4）. The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octabedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octabedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.     

Enhanced Photoactivity of Layered Nanocomposite Materials Containing Rare Earths, Titanium Dioxide and Clay

The nanocomposite materials containing rare earths, titanium dioxide and clay (RE/TiO2/Clay) were characterized and tested for the photocatalytic decomposition of formaldehyde. The results show that nanocomposite materials prepared by doping appropriate rare earth elements have better photocatalytic properties than that prepared by doping excessive rare earth elements. The photocatalytic mechanism of composite materials was studied by integrating the theory of photocatalysis with experiment results. Because the site of photocatalytic reaction was limited in the interspace of clay, photocatalytic reaction occurred by two steps: firstly, organic molecules dispersed into the interlayers of clay; secondly, organic molecules and photocatalyst of RE/TiO2 occurred photocatalytic reaction, resulting in forming carbon dioxide.     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

Preparing of Nano-Sized Power RE2O3(RE = La,Y,Gd) by Pyrolying Precursors

The precursors RE (HSal) 3 ( RE = La, Y, Gd; HSal = C6 H4 (OH) COO) were synthesized by the rheological phase reaction method. The mechanism and products of thermal decomposition of precursors was studied by using TG,DTA, gas chromatography-mass spectrometry (GC-MS). Nano-sized RE2O3 ( RE = La, Y and Gd) power were obtained by thermal decomposition of the precursors in air at 800 ℃. TEM measurement indicates that RE2O3 are spherical particles. The middle level diameter ( d50 ) of the particles are 19.3 ( La2O3 ) , 53.8 ( Y2O3 ) and 28.6 nm( Gd2O3 ) respectively by means of laser particles size analyzer.     

稀土配合物[REL3(4-picNO)H2O]的合成与表征

合成了2,3-二氯异丁酸根和4-甲基吡啶氮氧化物稀土三元配合物(RE=La、Ce、Pr、Nd、Sm、Eu).通过元素分析、红外、紫外、荧光、X射线粉末衍射、XPS、热分析以及摩尔电导等分析手段,确定了配合物的组成为[REL3(4-picNO)H2O](L= CH3C2H2Cl2COO -),并对它们的性质进行了讨论.     

Synthesis and Characterizations of Rare Earth Compounds RE(HCO 2) 3(HNO 2)(H 2CO 2)(RE=Y, Tb, Dy, Ho, Er, Yb, Tm)

Ｎｏｎｌｉｎｅａｒｏｐｔｉｃａｌｍａｔｅｒｉａｌｓｈａｖｅｂｅｅｎａｔｔｒａｃｔｅｄｍａｎｙｍａｔｅｒｉａｌｓｓｃｉｅｎｔｉｓｔｓａｎｄｃｈｅｍｉｓｔｓｆｏｒｔｈｅｉｒｉｍｐｏｒｔａｎｔｒｏｔｅｉｎｍｏｄｅｒｎｌａｓｅｒｔｅｃｈｎｏｌｏｇｙ．Ａ...     

Research and Development of Rare Earth Advanced Materials in China

ＲｅｓｅａｒｃｈａｎｄＤｅｖｅｌｏｐｍｅｎｔｏｆＲａｒｅＥａｒｔｈＡｄｖａｎｃｅｄＭａｔｅｒｉａｌｓｉｎＣｈｉｎａＷａｎｇＤｉａｎｚｕｏ（王淀佐），ＷａｎＱｕｎ（万群），ＹａｎｇＹｕｃｈｕｎ（杨遇春）（ＧｅｎｅｒａｌＲｅｓｅａｒｃｈＩｎｓｔｉｔｕｔｅ...     

稀土硝酸盐与希夫碱邻香兰素缩丙氨酸盐及邻菲咯啉三元配合物的合成与表征

合成了稀土硝酸盐与希夫碱邻香兰素缩丙氨酸盐(以KHL表示)及邻菲咯啉的三种固体三元配合物。通过元素分析、差热-热重、红外光谱、紫外光谱及摩尔电导分析等手段,确定配合物的组成为［RE(L)(Phen)(H2O)］NO3,(RE=Y,Nd,Sm)。并对它们的配位方式及某些性质进行了研究。     

Roles of rare earth oxide additives in millimeter-wave sintering of AlN

Roles of rare earth oxide (RE2O3) additives in millimeter-wave(MM) sintering of AlN were investigated from the standpoints of phase diagram, heating characteristics of rare earth oxides, and morphology of intergranular oxide phase. In the millimeter-wave sintering of AlN, densification temperature decreased with the decrease of the ionic radius of rare earth ion and was closely related with the eutectic temperature in the RE2O3-Al2O3 binary system. The lowest densification temperature in the millimeter-wave sintering of AlN with Yb2O3 additive was attributed to the largest heating rate of Yb2O3·Al2O3 binary oxide under millimeter-wave radiation. Furthermore, the lowest densification temperature could be attained while selecting the Yb2O3 content so as to form the intergranular phase with the eutectic composition in the Yb2O3-Al2O3 binary system. The result showed good agreement with the above mentioned during the sintering of Si3N4 with Yb2O3-Al2O3 additive. From TEM observation, it was verified that film-like intergranular oxide phase formed under millimeter-wave radiation was favorable for attaining high thermal conductivity in the Yb2O3 added AlNs.     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins

The effects of rare earth（RE）on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE（RE=La,Ce,Pr,Nd,Sm,Eu or Gd）,were prepared by the impregnation of the ZSM-5 type zeolites（Si/Al=64：1）with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B（Lewis acid/Brnsted acid）,but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.     

氯化铵焙烧法从中品位氟碳铈矿精矿提取稀土的研究

采用氯化铵焙烧法分解中品位氟碳铈矿精矿(REO～30%),热水浸取焙砂后,浸取液采用环烷酸全捞制备氯化稀土产品。研究了氯化反应温度、氯化剂用量及氯化时间等因素对稀土氯化率的影响。将中品位氟碳铈矿精矿与2倍氯化铵混合并加入少量添加剂,在480℃焙烧1.5h,焙砂用90℃热水浸取得氯化稀土浸出液,稀土收率为82.8%,浸出液进一步用环烷酸全捞,浓缩结晶得相对纯度为99.2%的氯化稀土产品。     

Rare earth modified Ni-Si catalysts for hydrogen production from methane decomposition

Different rare earth(RE=La, Ce, Pr, Nd, Sm, Y) and Cu modified nickel catalysts for hydrogen production from methane decomposition were synthesized by a sol-gel process and method. The catalysts were characterized or analyzed through Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) techniques. And the hydrogen production performance was also evaluated by a fixed-bed and micro-reaction technique with CH4→C+H2 as a probe reaction. The results showed that rare earth modification had played a great role for nickel catalysts, for example, smaller nickel particles, good thermal stability, high activity, etc. La was the best additive among rare earth modification. The SEM of rare earth modified catalysts showed ordered flower-like structure and rare earth modification made the nickel particles move to the surface of catalysts. In addition, the SEM of nano-carbons was also changed by rare earth modification with long, narrow nano-carbon fibers or tubes obtained. Solid carbon formation was prevented by rare earth modification.     

Preparation and characterization of complexes of RE^3＋ with furfural modified water-soluble chitosan

Degraded chitosan, with highly water-solubility, was obtained by the oxidation of chitosan with H2O2, and then reacted with furrural. The final product coordinated with the rare earth ions （RE^3＋ = Sm^3＋, Eu^3＋）, which led to the formation of the complexes. The prepared complexes were characterized with Infrared Spectroscopy （IR）, Ultra Violet （UV）, fluorescence, X-Ray Diffraction （XRD）, and Thermogravimetric-Differential Scanning Calorimetry （TG-DSC） measurements.     

Economical and Technical Indices of Decomposition Processes of Typical Rare Earth Minerals in China

The typical treatment processes we of main rare earth resources in China, especially the economical and technical indices of the minerals decomposition of such as ionic adsorptive rare earth deposit ore, bastnasite and mixed with monazite in Baotou, was presented. The dispersive ionic adsorptive rare earth deposit ore, which is enriched on valuable middle and heavy elements, concentrated by bicarbonate precipitation after exchanging with ammonium sulphate solution. Planting and waste liquid should be focused. Bastnasite and/or monazite, which is enriched light rare earth, centralized with high content and capacity,concentrated by gravimetric, magnetic, floating, then decomposed by calcinations and leaching. Waste liquid, gases and dregs should be treated properly. Investors interested in RE industry can find out the technical and economic characters and history of various RE minerals. Engineers and workers in RE industry can also find the differences of the plants, so as to make more efforts on improving management. However, solving environment protection problems for each process should be committed extraordinarily in order to make a sustainable development of RE industry.