钌基氨合成催化剂研究进展

钌基催化剂被称为继铁基催化剂之后第二代氨合成催化剂。文中介绍了钌基氨合成催化剂的载体、钌的母体化合物和促进剂的研究进展以及在钌基催化剂上氨合成反应动力学。     

钌基氨合成催化剂载体研究进展

钌基氨合成催化剂作为一种负载型催化剂,载体对催化剂活性有直接影响。本文对国内外广泛研究的活性炭载体．氧化物载体以及一些新型的载体作了评述,并对未来的研究方向进行了展望。     

钌基氨合成催化剂助剂研究进展

钌基氨合成催化剂由于具有低温、低压活性高的优点,而被誉为第二代氨合成催化剂.为了进一步节约能源,降低能耗,达到工业化的要求,国内外许多学者都在对钌基催化剂进行研究.而钌基催化剂中助剂的加入对催化剂活性有着非常大的影响.本文介绍了助剂的研究现状,对助剂的种类及其在催化反应过程所起的作用进行了总结,并介绍了助剂与载体之间的作用以及助剂我持次序的研究现状,旨在为我国进一步开发研制低温低压新一代氨合成催化剂提供参考.     

钌基氨合成催化剂的研究进展

钌基氨合成催化剂是一种在低温和较低压力下仍具有较高活性的负载型催化剂。综述了新型钌基氨合成催化剂的催化机理、国内外研究进展和工业应用情况,分析了催化剂中母体化合物、载体和促进剂等因素对催化剂活性的影响。钌基催化剂虽性能优良,但成本昂贵,因此探索新的活性组分、新的助剂与载体,研制出性能优良的钌基或非钌基催化剂是发展方向。     

新型钌催化剂和氨合成工艺

新型钌催化剂代替传统的铁系催化剂，不仅可以使氨的转化率及生产能力大大提高，而且对合成氨工业降低成本、降低消耗都有突破性进展。     

钌系氨合成催化剂开始产业化应用

总投资达8000万元的福建永安智胜化工有限公司钌催化氨合成氨生产示范工程的建设标志着钌系氨合成催化剂研究成果已进入产业化应用阶段。以往合成氨使用的是铁系催化剂，产量低，能耗高。钌系氨合成催化剂是继铁系催化剂后的第二代氨合成催化剂，由化肥催化剂国家工程研究中心经过5年攻关完成，已获得3项国家专利。     

氨合成钌基催化剂的研究进展

近年来,钌基氨合成催化剂因其高活性、高稳定性和反应条件温和成为研究热点。综述国内外氨合成钌基催化剂的研究进展,重点介绍钌基催化剂载体、助剂和前驱体对氨合成反应性能的影响。石墨化程度高、导电性能良好的碳载体或氧化物与碳的复合载体是氨合成反应的良好载体;碱金属和碱土金属类助剂通过改变活性金属表面静电场,起到电子助剂的作用,并且碱土金属对反应的促进作用优于碱金属,稀土金属Sm能够抑制碳载体的甲烷化反应;与Ru Cl3相比,Ru3(CO)12是氨合成反应的理想前驱体。简介以电子化合物为载体的钌基氨合成体系,负载钌的高比表面积电子化合物C12A7:e-是强大的电子供体,能够提高氮气在钌上的解离程度,并能可逆地储存氢,有效抑制氢吸附对钌表面的毒害,从而大大提高氨合成反应活性。进一步开发温和条件下非贵金属高效氨合成催化剂将具有重要的理论和现实意义。     

超低温低压钌系氨合成催化剂研究的新进展

介绍了国内外钌系氨合成催化剂的研究概况和凯洛格公司与英国石油公司合作开发的KAAP工艺,并结合我国的国情,提出了我国化肥行业应采取的对策和努力方向。     

助剂对钌基氨合成催化剂活性的作用研究

利用等体积浸渍法制备了活性炭负载钌基氨合成催化剂,考察了助剂Ba、K、Sm对催化活性的影响,探讨了其改善活性的调变规律。用TPD技术研究了氮在系列催化剂上的脱附行为。研究结果表明,助剂Ba、K、Sm的加入显著地提高了催化剂的活性,多助剂催化剂的活性明显优于单助剂催化剂。稀土金属氧化物Sm2O3除具有助催作用外,还有助于催化剂的热稳定性及钌的分散。在钌基氨合成催化反应中,N2 分子的活化离解是速控步骤。氮的脱附活化能愈低,催化活性愈高,其脱附活化能次序为Ru>Ru-Sm>Ru-K>Ru-Ba>Ru-Sm-K>Ru-Sm-Ba>Ru-Ba-K>Ru-Sm-Ba-K。     

氨合成催化剂卸出问题的探讨

本文介绍Kellogg氨合成塔就地改造后内件中催化剂的卸出,基于此,探讨了此类合成塔内件中催化剂的卸出方法和安全措施。     

The effect of cobalt on the reactants adsorption and activity of fused iron catalyst for ammonia synthesis

Modern adsorption study facilities as well as scanning electron microscopy, X-ray diffraction, Mössbauer spectroscopy and X-ray fluorescence spectroscopy were used to investigate the effect of cobalt on the adsorption of nitrogen, hydrogen and ammonia on the surface of cobalt modified iron fused catalysts. Adsorption studies were carried out at the temperature range specific for ammonia synthesis (385C). Activity tests were carried out under 10 MPa in the 350–450 C temperature range. Investigations were performed on the traditional multipromoted iron catalyst and on the series of catalysts prepared with addition of cobalt. Introduction of cobalt changed considerably the sample behaviour during activation and ammonia synthesis. Addition of cobalt promoted the iron catalyst for ammonia synthesis. The most active sample was that containing approximately 5.5 wt% Co. Cobalt changed the adsorption behaviour of the catalyst. Chemisorption of nitrogen is much higher for cobalt catalysts. Growth of nitrogen chemisorption and decrease of ammonia adsorption resulted in the growth of catalytic activity of cobalt catalysts in ammonia synthesis.     

反应条件对钌催化剂和铁催化剂的氨合成性能影响

Activated carbon-supported Ru-based catalyst and A301 iron catalyst were prepared,and the influences of reaction temperature,space velocity,pressure,and H2/N2 ratio on performance of iron catalyst coupled with Ru catalyst in series for ammonia synthesis were investigated.The activity tests were also performed on the single Ru and Fe catalysts as comparison.Results showed that the activity of the Ru catalyst for ammonia synthesis was higher than that of the iron catalyst by 33.5%-37.6% under the reaction conditions:375-400 °C,10 MPa,10000 h-1,H2︰N2 3,and the Ru catalyst also had better thermal stability when treated at 475 °C for 20 h.The outlet ammonia concentration using Fe-Ru catalyst was increased by 45.6%-63.5% than that of the single-iron catalyst at low tem-perature (375-400 °C),and the outlet ammonia concentration increased with increasing Ru catalyst loading.     

活性炭负载钌基氨合成催化剂的制备

利用浸渍法制备了活性炭负载钌基氨合成催化剂,讨论了影响钌分散度与氨合成催化活性的若干因素. 研究发现,若活性炭载体具有较大的比表面和较好的孔结构将有利于活性组分的分散. 同时,在浸渍之前,样品需在100～200 ℃干燥6～8 h. 催化剂各组分浸渍后对载体的表面结构影响不同,实验发现,Ba的添加可能为Ru的分散提供了合适的表面,而K主要填充于载体中孔并和Ru充分接触,并为Ru提供电子.同时要控制母体钌水溶液的pH值,并选用合适的浸渍顺序,方能达到较好的效果.     

Emission of excited potassium species from an industrial iron catalyst for ammonia synthesis

The angular dependence of potassium emission-desorption is studied from a fused iron catalyst of the type used for ammonia synthesis. The excited species (K^*, K _n ^* , etc.) and positive ions K⁺ have strongly different angular distributions. The bilobular distribution measured for ion desorption is concluded to be either due to excited atoms, so-called Rydberg atoms, or excited clusters. Both types of species have to desorb from the edges of the sample and become field ionized and deexcited just outside the sample, as reported in previous studies on an iron oxide catalyst. The peak in the normal direction measured for excited species is due to excited cluster formation outside the catalyst surface. Similarities with previous results for other catalysts are observed. The possibility that the promoter function of potassium in the ammonia synthesis is due to excited species is pointed out.On leave from Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland.     

ZA-5型催化剂在φ600mm、φ800mm氨合成塔中的应用

介绍了ZA - 5氨合成催化剂在6 0 0mm、80 0mm氨合成塔中的应用情况 ,并对其在使用过程中表现出来的优良特性作了总结     

FeO基氨合成催化剂的机械性能研

对不同铁比值（Fe²⁺/Fe³⁺）催化剂母体的机械强度进行了研究，考察了各种条件下FeO基A301型催化剂与Fe₃O₄基A110-2型催化剂的机械强度。研究表明，催化剂母体机械强度随着Fe²⁺/Fe³⁺）的增大而增强；相同条件下A301的机械强度优于A110-2，真密度是造成两者强度差异的主要原因；助催化剂的存在对强化FeO基催化剂机械强度有一定的积极作用。