重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。     

重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。     

Rare earth containing catalysts for selective catalytic reduction of NO_x with ammonia:A Review

Increasingly stringent regulations in many countries require effective reduction and control of NOx emissions. To meet these limits, various methods have been exploited, among which the selective catalytic reduction of NOx using ammonia as the reductant(NH3-SCR) is the most favored technology. High catalytic activity, N2 selectivity and resistance to deactivation by sulfur, alkaline metals and hydrothermal conditions are the optimal properties of a successful SCR catalyst. Rare earth oxides, particularly CeO2, have been increasingly used to improve the catalytic activity and resistance to deactivation of deNOx catalysts, both modifying traditional vanadium catalysts, and also developing novel catalysts, especially for low temperature applications. This review summarized the open literature concerning recent research and development progresses in the application of rare earths for NH3-SCR of NOx. Additionally, the roles of rare earths in enhancing the performance of NH3-SCR catalyst were reviewed.     

EDTA滴定法测定稀土铝中间合金中稀土总量

准确测定稀土铝中间合金中稀土总量,对于有效控制稀土铝中间合金的生产技术和产品质量具有重要意义。用400g/L氢氧化钠溶液溶解试样,此时,稀土与氢氧化钠反应生成氢氧化稀土沉淀,而铝与氢氧化钠反应后以偏铝酸根的形式留在了试液中,过滤,实现了铝与稀土元素的分离;用盐酸溶解沉淀,加入氢氟酸,此时稀土和氢氟酸反应生成氟化稀土沉淀,而铁与氢氟酸反应形成络合物留在溶液中,过滤,实现了干扰元素铁与稀土元素的分离;加入盐酸和高氯酸溶解沉淀,用抗坏血酸还原残留铁(III),乙酰丙酮溶液掩蔽残留的少量干扰元素铝,控制pH 5.5,以二甲酚橙作指示剂,用EDTA标准溶液滴定至溶液由红紫色变为亮黄色即为终点,建立了EDTA滴定法测定稀土铝中间合金中稀土总量的方法。将实验方法用于稀土铝中间合金(镧铝、钐铝、铒铝、钇铝)试样中稀土总量的测定,并在试样中分别加入不同量的于950℃马弗炉中灼烧过的高纯氧化镧、高纯氧化钐、高纯氧化铒和高纯氧化钇试剂进行加标回收试验,结果的相对标准偏差(RSD,n=11)不大于0.30%,加标回收率为99.6%~100.4%。选取镧铝、钐铝试样,按照实验方法测定其中稀土总量,并采用国标GB/T 31966—2015中的草酸盐重量法进行方法比对试验,测定结果基本一致。     

Recovery of rare earth and cobalt from Co-based magnetic scraps

The reuse of RE and cobalt in Co-based magnetic scraps was studied.The optimized feat lixiviated condition was:200 mesh,sulfuric acid dosage was of 1.4 times theoretic dosage,temperature was 80 oC and leaching time 1 h.The optimum technology conditions was:Na2S2O8 dosage was of 8 times theoretic dosage,oxidation temperature 80 oC,oxidation time 2 h and pH=4.5.Rare earth was precipitated by saturated(NH4)2C2O4 solution,after roasting of rare earth oxalate,rare earth oxide was received.Cobalt-iron residue was soaked by hydrochloric acid,the Fe(OH)3 was preferential solution,pH was adjusted to 1.4 by hydrochloric acid,Co(OH)3 did not dissolve,cobalt and iron were separated,after roasting of Co(OH)3,cobalt oxide was received.The total recovery of cobalt was found to be 97% and rare earths was 96%.     

稀土在氨合成催化剂中的研究与应用

介绍了稀土在氨合成催化剂中的研究情况,重点综述了稀土的作用机理及催化性能,还介绍了国内稀土氨合成催化剂性能及工业应用情况。     

海底稀土资源分离富集新工艺研究

研究了新型中重稀土资源,即海底沉积物中稀土分离富集新工艺。根据沉积物中稀土矿物相与脉石矿物相之间的表面物理性质差异以及不同矿物相在酸性溶液中的稳定性差异,研究了两段分离富集的新工艺流程。首先利用选矿方法将大部分脉石与稀土矿物进行初步分离,获得预富集了稀土的精矿,然后对稀土精矿进行二次化学富集,将杂质元素进一步去除,从而获得高品位的稀土中间产品。通过两次分离富集后,海底沉积物中约99%的杂质元素可被分离,稀土在中间产品中的品位可达6.41%,与原矿相比,稀土富集倍数达67倍,有利后续单个稀土的分离,同时中间产物酸耗可降低到原矿的1/12。     

Rare earth oxide modified Cu-Mn compounds supported on TiO₂ catalysts for low temperature selective catalytic oxidation of ammonia and in lean oxygen

Selective catalytic oxidation(SCO) of ammonia was carried out over Cu-Mn compounds catalysts modified with trivalent rare earth oxide Ce2O3 and La2O3 respectively.TiO2 was used as support and different ratio of O2 were tested in order to find an appropriate O2 concentration(vol.%),and the results showed that 1%O2(vol.%) was propitious to SCO of ammonia.The effects of the two rare earth oxides modified catalysts Ce2O3-Cu-Mn/TiO2 and La2O3-Cu-Mn/TiO2 on the catalytic activity and selectivity of ammonia oxidation were investigated under the reaction condition of 500 ppm ammonia,1%O2(vol.%),at the temperature from 125 to 250 oC.The results revealed the beneficial role of Ce2O3 and La2O3 in catalytic activity at low temperature and lean oxygen concentration,while the modification with Ce2O3 and La2O3 led to the negative influence on N2 selectivity.For the catalysts modified with Ce showed lower NO and N2O selectivity than the catalysts modified with La,then the effects of different Ce loadings on catalytic activity and selectivity were also considered,in combination with catalysts preparation methods,which include incipient wet impregnation,sol-gel method and co-precipitation.Results revealed that the catalysts prepared by sol-gel method obtained preferable catalytic activity compared with the others,reaching 99% ammonia at 200 oC,whereas 96% NO was detected.It also indicated that different catalyst preparation method significantly determined production distribution.     

Application of rare earths in fluid catalytic cracking: A review

The need for more active and hydrothermally stable fluid catalytic cracking(FCC)catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance catalyst activity and prevent the loss of acid sites during the FCC unit operation,especially when heavy residue with high metal content is used as feed.In this paper,a review was carried out to show the effects of rare earth elements on the structure,activity,and stability of FCC catalysts.Also,the use of rare earth elements as vanadium traps was analyzed in conjunction with the mechanism of catalyst deactivation by vanadium.The objective was to elucidate the interaction of vanadium species with the zeolite component of the FCC catalysts and the role of rare earth elements in countering the deleterious effects of vanadium on the FCC catalysts.     

Recovery of Rare Earths, Niobium, and Thorium from the Tailings of Giant Bayan Obo Ore in China

The recovery of rare earths, niobium, and thorium from Bayan Obo??s tailings has been investigated because the Bayan Obo ore is rich in rare earths and rich in niobium and thorium, but it is mined mainly as an iron ore and will be used up soon. By carbochlorination between 823?K (550?°C) and 873?K (600?°C) for 2?hours, 76 to 93?pct of rare earths were recovered from the tailings, which were much higher than those from Bayan Obo??s rare earth concentrate, together with 65 to 78?pct of niobium, 72 to 92?pct of thorium, 84 to 91?pct of iron, and 81 to 94?pct of fluorine. This suggests a cooperative reaction mechanism that carbochlorination of iron minerals (and carbonates) in the tailings enhances that of rare earth minerals, which is supported by a thermodynamic analysis. Subsequently, niobium separation from the low-volatile, ultrahigh iron chloride mixture was achieved efficiently by selective oxidation with Fe₂O₃. This process, combined with the best available technologies for separation of rare earths and thorium from the involatile chloride mixture and for comprehensively using other valuable elements, allows the ore to minimize radioactive waste and to use rare metal resources sustainably in the future.     

Processing of xenotime concentrate

Xenotime is a rare earth phosphate mineral which is a rich source of yttrium and heavy rare earths. Earlier experimental studies have been carried out in this laboratory on the chemical processing of hand-sorted xenotime obtained from the Bihar region to rare earth oxide intermediates. In addition to the deposits of xenotime in the Bihar region there are large volumes of placer deposits of rare earths containing both monazite and xenotime in the Siri river basin of Madhya Pradesh. Atomic Minerals Division is operating a pilot plant for the beneficiation of rare earths from these Siri river deposits. A low grade (typically analysing 45% light rare earth oxide, 3.4% Y₂O₃ and 2.3% heavy rare earth oxide) and intermediate grade (analysing 18.5% light rare earth oxide, 19.3% Y₂O₃ and 8.7% heavy rare earth oxide) concentrate is routinely being produced. The paper reports experimental studies involving alkali leaching and alkali fusion studies to recover rare earth oxide intermediates from low and intermediate grade deposits from Madhya Pradesh. It has been shown possible to extract almost 95% of rare earths by these processes.     

Physicochemical and isomerization property of Pt/SAPO-11 catalysts promoted by rare earths

Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...     

Improving Wear Resistance of the Ni-base Thermal Spray-Welding Coating Using Rare Earths

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The Rare Earth Aluminium Alloys in China

The development and application of rare earth aluminium alloys began in the 1960s in China.The represen-tative work was the usage of rare earth metals in alumino-silicon alloys for piston.In the 1970s,its initial stage.rare earths were used in enhanced AIMgSi alloy transmission line and FeCr Al alloy electric heating wire.Duringits developing period(from 1980 to 1985),in the field of smelting,after the electrolytic preparation of RE-Almaster alloys at relatively low temperature,a new technique was invented that rare earth compounds were addedto commercial aluminium electrowinning cell to produce RE-Al alloys directly.It opened the way for the appli-cation of rare earths in industry on a large scale.In the field of application,it was found that the addition ofrare earths could improve the conductivity and processing property of aluminium alloys.The application of rareearths to aluminium conductors and products had made a breakthrough progress.Since 1986,its golden age,thestudy,production and application of aluminium alloys containing rare earths have been developing at an amazingspeed,running neck and neck with the application of RE in agriculture,textile dyeing,and cast iron.     

Reduction of SO2 to elemental sulfur over rare earth-iron catalysts

With coal gas as a reducing agent, the catalytic reduction of SO2 to sulfur in the flue gas produced in metallurgical processes was studied over catalysts of rare earth-Fe/Al2O3 (REFe/Al2O3). The catalytic activity of the REFe/Al2O3 catalyst on the reduction of SO2 to sul-fur was investigated based on kinds and the contents of rare earths and different preparation method of the catalyst. Additionally, the mecha-nism of this catalytic reduction reaction was also explored. Results showed that different rare earth imposed different effect on the activity of the Fe/Al2O3 catalyst. Especially, the addition of Sm and Dy greatly improved the catalytic activity of Fe/Al2O3. The yield of sulfur over SmFe/Al2O3was increased to 86.62% at 360 ℃, which was 40.5% higher than that over Fe/Al2O3at the same temperature; and the sulfur yield over DyFe/Al2O3was increased to 91.62% at 400 ℃, 26.4% higher than that over Fe/Al2O3. The catalytic activity of REFe/Al2O3 was somehow dependent on the content of rare earth. For SmFe/Al2O3, the content of Sm was optimized to be about 1.0 wt.%. The rare earth catalyst prepared with different methods also showed varied activity. The sulfur yield over rare-earth transition metal catalysts follows the order: Sm and iron solution mixing impregnationSm first, then iron solution impregnationiron first, then Sm solution impregnation. The reaction mechanism of SO2 reduction to sulfur with coal gas was proposed to be an intermediate mechanism.     

熔融制样-X射线荧光光谱法测定轻稀土精矿中稀土总量

作为稀土工业的原料,稀土精矿中稀土总量的测定方法步骤多、流程长。实验采用熔融制样-X射线荧光光谱法测定轻稀土精矿中稀土总量,研究了制样和测量条件。准确称取6.000 0g无水四硼酸锂和偏硼酸锂混合熔剂(质量比2∶1)于铂黄坩埚中,以0.500 0g硝酸锂为氧化剂消除试样中还原物质对铂黄坩埚的侵蚀,称取0.600 0g稀土精矿试样,再于试样表面均匀覆盖0.500 0g氧化硼防止试样喷溅,滴加0.5mL 20mg/mL的溴化铵溶液作为脱模剂。将坩埚放进预加热到1 050℃的熔样机内熔融19min制备样片,可消除矿物效应、粒度效应及表面效应。通过各稀土元素X射线荧光谱线的选择减少谱线干扰,以经验系数法校正谱线干扰和基体效应,用稀土精矿标样建立各稀土元素校准曲线。各组分校准曲线的相关系数在0.991~0.999之间,试样重复测量的相对标准偏差(RSD)小于0.5%,稀土总量测定结果与重量法一致。方法的精密度和正确度能够满足生产要求。     

Recovery of rare earths from ion-absorbed rare earths ore with MgSO4-ascorbic acid compound leaching agent

The magnesium sulfate leaching technology for the ion-absorbed rare earths ore can solve the ammonia pollution problem existing in ammonium sulfate leaching process. However, the leaching capacity of magnesium sulfate is slightly weaker than that of ammonium sulfate, resulting in a bigger consumption of magnesium sulfate. In this paper, the MgSO_4-ascorbic acid compound leaching agent had been demonstrated to deal with the ion-absorbed rare earths ore. The ascorbic acid could form a stable coordination with rare earth ions, so that it can strengthen the leaching of ion-exchangeable phase.Moreover, ascorbic acid has a strong reductive property, it can leach the colloidal sediment phase rare earth as well. The present study investigates the effect of the initial pH and the composition of leaching agent on the rare earth leaching. It is determined that the rare earth leaching efficiency is 107.5% under the condition of pH 2.00,0.15 mol/L magnesium sulfate and 1.0 g/L ascorbic acid in leaching agent. In this case, the content of the ion-exchangeable phase and colloidal sediment phase rare earth in the leaching residues are both only 0.02‰. The leaching efficiency of colloid sediment phase rare earth can be 85.7%,so that the Ce partition in the leaching liquor increases to be 5.77%. The magnesium-ascorbic acid compound leaching agent is proposed to be a promising choice to deal with the ion-absorbed rare earths ore, which can realize the efficient leaching, low consumption of MgSO_4 and environmentally friendly leaching.     

Examination of Plasma Nitriding Microstructure with Addition of Rare Earths

Medium-carbon alloy steel was plasma nitrided with rare earths I_a, Ce and Nd into the nitriding chamber respectively. The nitriding layer microstructures with and without rare earths were compared using optical microscope, normal SEM and high resolution SEM, as well as TEM. It was found that the extent of the influence on plasma nitriding varies with different contents of rare earth. The effect of plasma nitriding is benefit from adding of Ce or Nd. The formation of hard and brittle phase Fe2-3N can be prevented and the butterfly-like structure can be improved by adding Ce or Nd. However, pure La may prevent the diffusion of nitrogen and the formation of iron nitride, and reduce the depth of diffusion layer.     

Effects of Light and Heavy Rare Earths on Anti-Degradation of Nodular Cast Iron

The effects of rare earths with different contents on anti-degradation of Y base heavy rare earths-magnesium and cerium base light rare earths-magnesium nodular cast iron were studied. Curves of the relationship between the spheroidization grade of liguid iron treated by different nodulizers and holding time were obtained. The results show that the more the remains of the rare earth, the longer the anti-degradation time, the liquid iron was treated either by Y-Mg-Si or by Ce-Mg-Si nodulizer. When the rare earth remains are above certain quantity, the spheroidization grade starts to decline. When liquid iron treated by either Y-Mg-Si or Ce-Mg-Si nodulizer with proper remains of rare earths about 0.04% 0.06%（mass fraction）, the anti-degradation is the best, and the remains of Mg being about 0.04% -0.07% （mass fraction）. Rare earths-Mg nodulizer with moderate RE remains is better than that of Mg-Si nodulizer in anti-degradation property. However, Y-Mg-Si nodulizer with moderate remins of Re is better than Ce-Mg-Si nodulizer. Sometimes Ce-Mg- Si nodulizer can be used for the production of heavy section nodular cast iron.     

掺杂稀土BaTiO3的制备及镍基催化剂的活性

采用柠檬酸盐法和溶胶-凝胶法合成出稀土掺杂的BaTiO3,并考察了稀土离子掺杂对BaTiO3颗粒粒径的影响。测定了掺杂BaTiO3的比表面积、晶相、粒度等粉体性能,指出稀土离子有抑制BaTiO3晶粒长大的作用。稀土掺杂的BaTiO3作镍基催化剂载体,以CO2/CH4重整制合成气为探针反应,评价了这些催化剂的催化活性,实验表明掺杂稀土有助于提高催化活性。