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。     

Effect of rare earth elements(La,Y,Pr)in multi-element composite perovskite oxide supports for ammonia synthesis

A series of BaCe0₃modified with different rare earth elements(La,Y,Pr)were synthesized by coprecipitation and calcination and the effect of rare earth elements for catalytic ammonia synthesis under mild conditions was studied.The ammonia synthesis performance tests show that 2.5%Ru/BaCe_0.9La_0.1O_3-δcatalyst(All the percentages of Ru in this article are in mass fraction)exhibits the highest ammonia synthesis rate(34 mmol/(g·h))at 3 MPa,450℃,and no sign of deactivation after 100 h of reaction.H₂-TPR and XPS analyses indicate that the introduction of La increases the amount of oxygen vacancies of the catalyst,which is beneficial to increasing the electron density of Ru surface.HRTEM analysis shows that the Ru particle size is reduced greatly after La is introduced,which facilitates the catalyst generating more Bs-type sites(active sites of Ru species for N=N dissociation).CO₂-TPD analysis indicates that BaCe_0.9La_0.1O_3-δhas stronger basicity,which promotes electrons transfer from support to Ru.This work provides an effective method for design and synthesis of Ru-based multi-element composite perovskite oxide catalysts.     

Review on catalytic roles of rare earth elements in ammonia synthesis:Development and perspective

Ammonia(NH3)is mainly produced via the Haber-Bosch process.It was discovered that the performance of a wide variety of catalysts in NH3 synthesis could be considerably enhanced by the addition of rare earth elements(REEs).As a result,catalysts promoted by REEs,especially the Ru-based ones have been extensively investigated.In this review,we summarize the progress of utilizing REEs for ammonia synthesis and outline the prospects of using them in the design and development of highly efficient and stable catalysts for ammonia synthesis.     

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.     

稀土元素对钛合金蠕变性能影响规律综述

钛合金因其所具有的高比强度和耐腐蚀等优异性能而在航空航天、舰船及石油化工等领域得到广泛应用.蠕变性能是其在高温条件下使用的一项重要指标，添加稀土元素被认为是改善钛合金高温蠕变性能行之有效的方法之一.首先介绍了稀土元素在钛合金中的应用概况，总结了稀土对钛合金综合力学性能的影响.重点分析了Nd、Y、Gd、Er、La等稀土元素的含量、添加形式及制备方法等对钛合金蠕变性能的影响规律，总结了稀土元素影响钛合金蠕变性能的微观机理.提出通过研究稀土Sc对钛合金中硅化物析出过程及其分布的影响规律，进而阐明其抗蠕变机理，提高合金蠕变性能，为设计具有更加优异性能的钛合金材料提供基础理论支撑，是稀土改性钛合金的研究方向之一.      

稀土在甲烷部分氧化制取合成气中的应用研究

稀土（La,Ce,Pr,Nd等）通常可以作为催化剂载体、助剂或与其它元素形成固溶体,成为催化剂的重要组成部分。文中系统地介绍了稀土在甲烷部分氧化（CPOM）制取合成气中的相关应用,重点分析了稀土作为催化剂载体、助剂、固溶体等在催化部分氧化制取合成气中的应用,并对其在CPOM中未来前景做出展望。     

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.     

Rare earth oxides and their supported noble metals in application of environmental catalysis

Volatile organic compounds(VOCs),methane,carbon monoxide,soot,automotive exhaust,and nitrogen oxides are harmful to the atmosphere and human health.It is urgent to strictly control their emissions.Heterogeneous catalysis is an effective pathway for the removal of these pollutants,and the critical issue is the development of novel and high-performance catalysts.In this review,we briefly summarize the preparation methods,physicochemical properties,catalytic activities,and related reaction mechanisms for the above pollutants removal of the rare earth oxides,mixed rare earth oxide,rare earth oxidesupported noble metal,and mixed rare earth oxide-supported noble metal catalysts that have been investigated by our group and other researchers.It was found that catalytic performance was associated with the factors,such as specific surface area,pore structure,particle size and dispersion,adsorbed oxygen species concentration,reducibility,reactant activation ability or interaction between metal nanoparticles and support.Furthermore,we also envision the development trend of such a topic in future work.     

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.     

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.     

Effect of barium and potassium promoter on Co/CeO2 catalysts in ammonia synthesis

The Co/CeO₂ catalysts promoted with Ba or K were prepared to study the effect of promoter on the catalytic performance of ammonia synthesis. The results show that the presence of Ba or K promoter changes the properties of CeO2-supported Co catalysts including the surface area, the crystallite size and the morphology of CeO₂, the reduction degree of cobalt species and the adsorption performance of hydrogen and nitrogen. As a consequence, the samples promoted with an appropriate amount of Ba show higher ammonia synthesis rates, while the catalysts with high Ba loading or K promoter all exhibit low catalytic activities.     

A novel fused iron catalyst for ammonia synthesis promoted with rare earth gangue

Rare earth gangue, which mainly consists of mixtures of light rare earths such as lanthana, ceria, neodymium oxide and praseodymium oxide, was used as the promoter of fused iron catalysts for ammonia synthesis. The result showed that the activity of the catalyst promoted with rare earth gangue was comparable with those of commercial iron catalysts with high amount of cobalt. The role of rare earths was owed to their advantages for favoring the deep reduction of the main composite in catalyst, i.e., iron oxide. This fmding indicated that the use of rare earth gangue could decrease the content of cobalt or even completely replace cobalt, which was used to be regarded as unsub- stitutable promoters for high performance ammonia catalyst; therefore, the cost of fused iron catalysts would decrease significantly.     

Catalytic decomposition of ethyl acetate over La-modified Cu-Mn oxide supported on honeycomb ceramic

The La-modified Cu-Mn spinel oxide was successfully coated onto honeycomb ceramic by a washcoating method for complete catalytic decomposition of ethyl acetate.The La-modified Cu-Mn oxides were characterized by X-ray diffraction,X-ray fluorescence,H_2-temperature programmed reduction,Brunauer-Emmett-Teller method,field-emission scanning electron microscopy and high-resolution transmission electron microscopy.The effects of different precipitants and rare earth doping on the structure and catalytic performance of the catalysts were investigated.The results show that the CuMn_2 O_4 spinel with(NH_4)_2 CO_3 as a precipitant can form a larger specific surface area and a suitable pore size,which is beneficial to the absorption of ethyl acetate.Although the rare earth doping does not significantly change the crystal phase structure of the catalyst,it improves its reducibility and lowers the temperature of the catalytic decomposition.With respect to the catalytic decomposition of ethyl acetate,the rare earth-modified Cu-Mn oxide supported on honeycomb ceramic shows excellent catalytic performance with 100% conversion under the conditions of 239℃,space velocity of 12500 h~(-1) and1000 ppm.And the ethyl acetate removal rate is still 100% after 1440 min of continuous reaction.     

Effect of hydration on the surface basicity and catalytic activity of Mg-rare earth mixed oxides for aldol condensation

Magnesium and rare earth mixed oxides (Mg₃REO_x (RE = La, Y, Ce)) were prepared and characterized by X-ray diffraction (XRD), N₂ adsorption–desorption, infrared spectra and microcalorimetry of CO₂. The results reveal that the Mg₃CeO_x catalyst is present in the form of Mg-Ce-O solid solution, while the Mg₃LaO_x and Mg₃YO_x catalysts are probably rare earth oxides dispersed on MgO surface. As a result, among the calcined Mg₃REO_x catalysts, the Mg₃CeO_x catalyst presents the highest rate constant for acetone aldolization, which is well correlated to its more homogeneous distribution of basic sites. In contrary, the Mg₃YO_x catalyst exhibit the lowest catalytic activity for acetone aldolization. Upon hydration pre-treatment, the basic properties on the surface of the Mg₃REO_x catalysts were changed markedly. The Mg₃YO_x catalyst after hydration treatment shows the highest amount of basic sites on catalyst surface, and then exhibits the highest activity among the hydrated Mg₃REO_x catalysts. These results make it possible to fine-tune basic sites for acetone aldolization.     

稀土元素定位在生物体系中的应用

弄清稀土元素在细胞中作用的部位,对理解其生物效应具有极其重要的意义。同时,稀土元素本身具有一些特殊的化学性质,利用细胞定位技术,可以更有效地对生物系统研究。     

Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.     

Ce-Fe-Mn ternary mixed-oxide catalysts for catalytic decomposition of ozone at ambient temperatures

Ce-modified Mn-Fe mixed-oxide catalysts were prepared by a citric acid sol-gel method and characterized by X-ray diffraction,Raman,N_2 adsorption-desorption,infrared spectra H_2 temperature-programmed reduction and thermogravimetric analyses.Their catalytic properties were investigated in ozone(O_3)decomposition reaction.Results show that the small amount of rare earth metal Ce added during Mn-Fe(FM) mixed-oxide synthesis greatly improves the catalytic performance in O_3 decomposition.Among the prepared catalysts.the C_(0.04)(FM)_(0.96) mixed-oxide catalyst exhibits the highest catalytic activity and stability.The O_3 conversion over C_(0.04)(FM)_(0.96) is 98% after 24 h reaction at 25℃ under dry condition,and that over FM decreases to 90% after 16 h reaction.At 0℃,the O_3 conversion over C_(0.04)(FM)_(0.96) is 95% after 7 h reaction under dry condition.and that over FM slows down to 70%.Under humid condition(RH 65%),the O_3 conversion over C_(0.04)(FM)_(0.96) is 63% after 6.5 h reaction at 25℃.while that over FM decreases to 55%.When Ce is doped into Mn-Fe mixed oxides,the small amount of Ce enters the crystal lattice of MnO_2.and partial Fe is separated to form Fe_2O_3.This changes cause lattice distortion and increase defects and enable the as-synthesized Ce-Fe-Mn ternary mixed-oxide catalysts to acquire additional oxygen vacancies and increase their specific surface area,thereby increasing the number of reaction sites and enhancing the catalytic performance of the catalysts forO_3 decomposition.     

Use of rare earth elements in single-atom site catalysis:A critical review——Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Rare earth metals are strategic resources with potential applications in optics,metallurgy and catalysis.In recent years,single-atom site catalysts(SASCs) have attracted increasing attention owing to their 100%atom efficiency and unique catalytic performances.Over the past decade,rare earth elements,including rare earth metals and their oxides,have shown great potential in SASCs.However,systematic analyses of data are still handful.In this mini-review,the use of rare earth metals and their oxides in SASCs was summarized and the results are discussed.A particular focus was paid to the synthetic strategies,characterization of rare earth-containing SASCs,and applications as catalysis supports,promoters and active sites.Current issues faced by rare-earth metals and their oxides in SASCs,as well as future prospects were also provided.     

Extraction and back-extraction behaviors of 14 rare earth elements from sulfuric acid medium by TODGA

The unique physical and chemical properties of rare earth elements lay the foundation for their extensive application. N,N,N',N' Tetra-octyl-3-oxopentanediamide(TODGA) is excellent in its ability of extracting rare earth elements and it is favored for green initiative. In this paper, the extraction and back-extraction of14 rare earth elements by TODGA were studied. Experiments show that in conditions of 6 mol/L sulfuric acid, the extraction temperature of 25 ℃,the phase ratio of 1:1 and 0.04 mol/LTODGA(aviation kerosene as the diluent), the extraction rates of 14 rare earth elements including lanthanum, cerium, praseodymium,neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium were 99.00%-99.73%. Mixed with hydrochloric acid and nitric acid(HCl 3.5 mol/L, HNO_30.5 mol/L), the recoveries of the 14 rare earth elements are 91.52%-99.91% when the extraction temperature is 25 ℃ and the ratio is 1:1. The following application is based on the optimum conditions above with practical samples(from the roasting production line of China North Rare Earth High-tech Company Limited) for extraction and back-extraction experiments. Experiments show that TODGA has excellent enrichment effect on 14 rare earth elements, the extraction rates are 91.36%-99.80%, the back-extraction rates are 87.29%-99.64% and the total recoveries are 81.19%-99.44%.     

微生物技术在稀土资源利用中的研究进展

主要介绍了稀土资源的重要作用及利用现状,对我国的稀土矿分布及特征进行概述,并提出稀土开采存在的问题及微生物采矿的优势。回顾利用微生物进行稀土矿开采的发展进程,总结其研究进展,介绍微生物采矿作用机理的研究,主要包括微生物浸出、吸附和积累稀土元素机理的相关研究,以及稀土矿采矿微生物的分离方法及种属分布等。以中国白云鄂博矿床和澳大利亚Mount Weld矿床中的矿石为例,说明微生物对矿石中稀土元素的提取作用。简述微生物对废弃物中稀土元素的回收作用,及微生物利用稀土元素技术将面临的挑战,并对其未来进行了展望。