改进氨分解工艺 延长催化剂寿命

我厂的氨分解装置采用的是热催化技术，即在还原氛围下，氨和氰化氢经高温催化分解成氮、氢和一氧化碳。因氨分解炉是核心设备，仅炉内所装填催化剂的价值就高达１００万元，在保证氨分解效率的前提下，如何延长催化剂的使用寿命，则是我们日常工作的重点。１氨分解催化剂的损耗原因我们所用的氨分解催化剂是以氧化镁为载体，镍是主要活性成分。生产实践表明，在氨分解过程中造成催化剂损耗的原因有如下几方面。（１）虽然氨的分解需在高温下进行，但当温度超过１２００℃时，会使镍蒸汽压过高而加快镍的流失。当炉温低于９００℃时，则易发…     

蒸氨、氨分解工艺设备优化改造

通过对蒸氨、氨分解系统一段时间的运行操作分析,发现原料氨水在蒸氨塔内经蒸汽蒸吹后的氨汽在分缩器的冷却过程和氨汽在分解炉中经高温和催化剂的作用被催化分解,生成氮、氢和一氧化碳的过程中存在的问题,针对这些问题采取了优化改造。     

延长氨分解器催化剂使用寿命的措施

目前,不少焦化厂的煤气净化工艺中,用催化分解炉在１０００～１２００℃下将氨分解成氮气和水,催化剂是由氧化镁作载体的负载活性镍构成的固体催化剂,氨分解炉内一般需充填８～１０ｔ催化剂,而价值高达上百万元。为此,如何延长催化剂的使用寿命,就成为降低生产成本重要环节。１影响催化剂寿命的因素氨气进入氨分解炉后,在空速一定时,氨的分解率与催化剂所含的活性镍有关,一般国产催化剂使用一年左右后,就会因活性镍减少,难以达到要求的氨分解率而更换新催化剂。催化剂失活的原因有以下两个方面：(1)镍损耗。主要是升华损耗,由…     

氨分解催化剂的研究现状及发展方向

氨分解催化剂广泛应用于低温氨分解制氢和环保领域,本文介绍了国内外氨分解催化剂的研究现状,对活性组分、载体及助剂对催化剂活性的影响进行了详细评述,并展望了氨分解催化剂的发展方向。     

氨分解制氢催化剂改性研究进展

在氨分解制氢技术中催化剂的选取尤为重要,其组成、形貌结构、载体、助剂等均能影响催化剂活性发挥。本文综述了近几年国内外氨分解制氢催化剂的改性研究现状,对催化剂的形貌结构变化、不同载体的影响、助剂的添加、矿石及工业废品在氨分解中的应用进行了详细的介绍,指出有效发挥催化剂和载体、助剂等之间的协同作用,改善外部条件,对于实现氨分解制氢具有很好的潜在实用价值,进一步设计出低压、低温、高活性氨分解的新型催化剂,降低能量消耗是未来氨分解催化剂的研究方向。     

半导体悬浮体系光催化分解有机磷化合物

本文研究了半导体悬浮体系光催化分解有机磷化合物的条件,只有在光照、催化剂和氧同时存在的条件下才能有效地光催化分解有机磷化合物;测量了两种有机磷化合物在各种半导体催化剂上的分解速率,反应速率与催化剂的种类和表面性质有关;对光催化分解马拉硫磷的反应机理进行了初步探讨。     

V-Ti基脱硝催化剂去除汞和PCDDs/PCDFs的研究现状

将柔软纤维与折皱钢网复合制成波纹式支撑骨架,将V-Ti基脱硝催化剂负载到波纹式支撑骨架上制成整体波纹式脱硝催化剂。介绍V-Ti基波纹式整体脱硝催化剂的主要制备工艺、优点以及国内外对V-Ti基波纹式整体脱硝催化剂的研究现状;对V-Ti基脱硝催化剂与贵金属脱硝催化剂的制造成本以及PCDDs/PCDFs催化分解效果进行对比,两者具有相同的催化分解效果,V-Ti基脱硝催化剂成本低得多;活性组分、V质量分数以及活性温度不同,V-Ti基脱硝催化剂催化分解PCDDs/PCDFs的效果也不同,催化分解率最高可达97.7%;研究者得出V-Ti基脱硝催化剂催化氧化Hg0的不同效果,介绍V-Ti基脱硝催化剂催化氧化Hg0的研究现状。     

低温催化脱硝技术的研究进展

面对日益严重的环境问题,燃煤烟气催化脱硝技术得到了较快发展。针对目前应用较为广泛的选择性催化还原脱硝技术,本文从催化脱硝技术的机理出发综述了低温催化脱硝方面的研究进展,将低温催化脱硝技术分成两大类:低温氨法选择性催化还原脱硝技术和低温非氨法催化脱硝技术。在低温氨法选择性催化还原脱硝技中总结了金属氧化物催化剂、分子筛催化剂以及碳基催化剂等的反应机理和反应过程,揭示了影响脱硝效率的各种因素;低温非氨法催化脱硝技术中从反应方式出发,总结了NO_x催化裂解技术、HC-SCR技术、NO_x吸附-还原技术以及CO催化脱硝技术的研究进展,并对反应影响因素进行了综述。探索了各种催化剂的优势和不足之处:低温NH₃-SCR技术具有选择性高、效率高的特点但是其还原剂价格较贵且存储运输较为困难;低温非氨法催化脱硝技术选择性差、效率低,但是还原剂价格低廉、易于制备,且在工艺方面改进时可以达到要求的效率。在此基础上本文展望了未来低温催化脱硝的研究方向:在降低脱硝成本的情况下改善催化脱硝工艺,大力发展氮氧化物吸附还原等技术。     

非热等离子体协同锰铁双金属催化剂直接催化还原NO

传统氨选择性催化还原（NH₃-SCR）法在大气污染物NO的脱除中得到广泛应用，但仍存在催化剂有毒、操作温度高及氨逃逸等缺点，不能满足日益增多的低温应用场景和更高的环保要求。本文采用浸渍法制备了SBA-15分子筛负载的锰铁双金属催化剂，研究了非热等离子体协同催化剂低温下直接催化还原NO的性能。活性测试结果表明，室温下等离子体输出电压为12kV时，等离子体协同催化的NO转化率达到97.8%。表征结果显示等离子体协同反应前后催化剂的孔道结构和物理形貌未见明显变化。在线质谱分析结果表明，等离子体协同催化作用下，NO被直接分解为N₂和O₂。由机理分析可知，不同价态Mn物种间的电子传递削弱了催化剂表面吸附态NO分子中N—O键，使得等离子体分解NO的能耗下降。     

镍基氨分解制氢催化剂的制备及性能

用浸渍法制备Ni/Al_2O_3和Ni/xMo-Al_2O_3催化剂,以氨分解为模型反应,考察Ni负载量、焙烧温度、溶剂和助剂等合成条件对催化剂催化性能的影响,通过XRD和TG-DTG表征方法对催化剂进行表征。结果表明,最佳合成条件:Ni负载质量分数为16%,焙烧温度350℃,采用丙酮为溶剂制备的Ni/Al_2O_3催化剂具有较好的催化活性。500℃添加质量分数3%的助剂Mo可以使Ni/Al_2O_3催化剂的活性显著提高39%,Ni/3%Mo-Al_2O_3催化剂的氨分解率达93.5%。     

Promoted Ru on high-surface area graphite for efficient miniaturized production of hydrogen from ammonia

Promoted Ru/C catalysts for decomposition of ammonia are incorporated into micro-fabricated reactors for the first time. With the reported preparation technique, the performance is increased more than two orders of magnitude compared to previously known micro-fabricated reactors for ammonia decomposition. The catalytic activities for production of hydrogen from ammonia are determined for different promoters and promoter levels on graphite supported ruthenium catalysts. The reactivity trends of the Ru/C catalysts promoted with Cs and Ba are in excellent agreement with those known from earlier studies of both ammonia synthesis and decomposition, and it is shown how proper promotion can facilitate ammonia decomposition at temperatures below 500 K.     

氨分解制氢催化剂研究进展

随着环保法规日趋严格,清洁氢能的生产和应用引起关注,氨分解制氢是其中重要途径之一。综述Ru、Ni和Fe等氨分解催化剂的研究进展,Ru催化剂具有较高的催化活性,但由于资源有限和价格昂贵等因素使其在工业应用方面受到限制。以Fe和Ni为代表的非贵金属催化剂资源丰富,价格低廉,氨分解反应转化率高,具有潜在的工业应用前景。我国独创的新一代Fe_(1-x)O基新型熔铁催化剂是目前世界上活性最高的氨合成催化剂,根据微观可逆性原理,新型熔铁催化剂也是氨分解反应活性最好的制氢催化剂。     

Study of the Kinetics of Ammonia Synthesis and Decomposition on Iron and Cobalt Catalysts

Activity of cobalt and iron catalysts in ammonia synthesis was determined under a pressure of 10 MPa and at the temperature range of 673–823 K, in a six-channel integral steel reactor. The catalytic ammonia decomposition was studied in a differential reactor under the atmosphere of low concentration of ammonia (<6%) in the temperature range of 673–823 K under atmospheric pressure. The determined values of the activation energy for the ammonia synthesis reaction over cobalt and iron catalysts are 268 and 180 kJ/mol, respectively, whilst for the ammonia decomposition reaction they are equal to 111 and 138 kJ/mol. The cobalt catalyst showed lower activity than a commercial iron catalyst in ammonia synthesis reaction. The cobalt catalyst turned out to be more effective in ammonia decomposition reaction than the iron one.     

Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications

Catalytic decomposition of ammonia has been investigated as a method to produce hydrogen for fuel cell applications. The absence of any undesirable by-products (unlike, e.g., CO_x, formed during reforming of hydrocarbons and alcohols) makes this process an ideal source of hydrogen for fuel cells. In this study a variety of supported metal catalysts have been studied. Supported Ru catalysts were found to be the most active, whereas supported Ni catalysts were the least active. The supports were found to play a profound role in the ammonia decomposition process. The activation energies for the ammonia decomposition process varied from 17 to 22 kcal/mol depending upon the catalyst employed. The activation energies of the supported Ir catalysts were found to be in excellent agreement with our recent studies addressing ammonia decomposition on single crystal Ir.     

氨分解制氢镍基催化剂研究进展

氨分解制氢清洁高效,易于工业化使用,是一种极具前景的便携式制氢方法。镍作为氨分解非贵金属催化剂中性能最好、应用最广的催化剂,但仍存在低温活性低、易烧结等问题亟需改进。本文概括了氨分解反应的反应机理、动力学和热力学,综述了近年来国内外氨分解镍基催化剂的研究现状。研究者从镍金属活性中心调控出发进行研究,发现调节镍粒子尺寸、加入第二金属(Fe、Co、Mo等)、载体(Al₂O₃、SiO₂、分子筛等)、助剂(碱土金属、稀土金属等)以及设计核壳结构进行调控,可提高镍金属的分散性和抗烧结能力。本文在以上基础上提出了镍基催化剂的改进措施和未来发展方向,以期为进一步设计出低温高活性镍基催化剂提供依据。     

Recent advances in catalysts for hot-gas removal of tar and NH3 from biomass gasification

Biomass gasification produces a low to medium-BTU product gas (or syngas) containing primarily CO₂, H₂, CO, CH₄ and (C₂ + C₃), as well as some contaminants such as tars, NH₃, H₂S and SO₂. In order to achieve better efficiencies of the syngas applications, these contaminants must be removed before the syngas is used for internal combustion, gas engines, and in particular for fuel cells and methanol synthesis. Compared with the wet scrubbing technology, hot-gas cleanup technology to remove tar, ammonia and other contaminants at the “hot” state is more advantageous with respect to energy efficiencies. This paper provides an overview on recent advances in catalysts for hot-gas removal of tar and ammonia from biomass gasification. The review focuses on the recent development and applications of dolomite catalysts, iron-based catalysts, nickel and other metal supported catalysts, and the novel carbon-supported catalysts for hot-gas tar removal and ammonia decomposition. The barriers in applications of hot-gas cleanup processes and catalysts for full-scale biomass gasification, and areas for future research, are also discussed.     

Catalyst decomposition during temperature programmed desorption of bases from promoted sulfated zirconias

Results from temperature programmed desorption of ammonia, pyridine, and benzene from sulfated zirconia catalysts promoted with Fe, Mn, and Ni are compared. Without adsorbates, catalysts are thermally stable below 900 K. With adsorbates, catalysts decompose partially or completely between 700 and 900 K. It is shown that previously reported conclusions regarding acid strength distributions for promoted sulfated zirconia catalysts that were based on the results of ammonia and benzene thermal desorption studies are likely incorrect because the decomposition of adsorbates and the catalyst were not considered.     

混合法制备铁钌复合催化剂的研究

以维氏体铁催化剂为载体,以十二羰基三钌为钌的前驱体,采用固相混合法制备系列铁钌复合催化剂,考察十二羰基三钌的分解温度、热分解气氛以及钌负载量对催化剂活性的影响。采用扫描电子显微镜和热重分析等考察催化剂的表面性质与催化活性关系。结果表明,采用固相混合法得到的铁钌复合催化剂用于氨合成反应活性得到提高,在氮气气氛中,十二羰基三钌分解温度为120℃,钌负载质量分数为0.6%时,催化剂活性较好。