耐硫变换工艺的开发与应用

本回顾了耐硫变换工艺的开发过程，论述了新工艺的独特优越性能，列举几种主要耐硫变换催化剂的物理性能与工业上使用条件；介绍托普索公司开发的SSK耐硫变换催化剂在工业生产上适用的工艺参数；并对国产耐硫变换催化剂在煤加压与煤常压气化制合成氨原料气实际应用的工艺条件进行说明与讨论，期望今后耐硫变换新工艺在工业生产上发挥更大的作用。     

新型耐硫变换催化剂研究及工业应用

RSB-M型耐硫变换催化剂是新型的可适用于加压气化工艺中变换工段的耐硫变换催化剂,长周期工业侧线试验表明,RSB-M型耐硫变换催化剂在活性及结构稳定性方面良好,适用范围较宽,可适用于不同的压力、汽气比及空速条件,工业应用及不同位置催化剂样品的分析表明,RSB-M型耐硫变换催化剂活性及抗水合性能明显优于工业催化剂。     

CO变换催化剂的研究进展

介绍了国内外CO中(高)温变换催化剂、低变催化剂及耐硫变换催化剂的现状及研究进展。高效节能型变换工艺将是变换工艺的发展方向,开发低温、高活性和稳定性的变换催化剂将相应成为研究的主要目标。     

Co-Mo系耐硫变换催化剂硫化的探讨

介绍了耐硫变换催化剂的硫化原理及硫化工艺,阐述了硫化条件对耐硫变换催化剂活性的影响。     

Co-Mo系耐硫变换催化剂硫化的探讨

介绍了耐硫变换催化剂的硫化原理及硫化工艺，阐述了硫化条件对耐硫变换催化剂活性的影响。     

粉煤气化工艺耐硫变换难题有解

航天粉煤气化工艺耐硫变换技术研讨会日前在青岛举行。专家指出,耐硫变换技术是目前粉煤气化工艺能否成功用于合成氨或甲醇生产的关键,粉煤气化应优先选定节能型低水气比耐硫变换工艺。同时,催化剂性能与装填量是变换反应床层温度控制的重要环节。借鉴这一思路,壳牌粉煤气化工艺和航天粉煤气化工艺的耐硫变换难题已有了解决方案。     

QCS型耐硫变换催化剂的应用

<正>0前言因气化方法不同,制得的原料气中CO含量也不同,进而变换工序采用的耐硫变换工艺也大不相同,变换催化剂种类多样。即使是同一种气化工艺,由于变换压力、原料气中的H2S含量、水气比、后续工段微量CO及H2S脱除方法的不同,采用的耐硫变换工艺也不完全相同。特别是近     

新型耐硫一氧化碳变换催化剂的工业应用

介绍新型耐硫变换催化剂ＱＣＳ－０１工业侧线和工业应用结果。试验和应用结果表明，ＱＣＳ－０１是一种能够在高压、高水蒸汽分压和工艺气体硫含量宽的条件下使用的宽温宽硫型的钴钼耐硫变换催化剂，主要性能优于国外名牌工业钴钼耐硫变换催化剂。     

新型耐硫一氧化碳变换催化剂的工业应用

介绍新型耐硫变换催化剂ＱＣＳ－０１工业地线试验和工业应用结果。试验和应用结果表明，ＱＣＳ－０１是一种能够在高压、高水蒸汽分压和工艺气体硫含量宽的条件下使用的宽温宽硫型的钴钼耐硫变换催化剂，主要性能优于国外名牌工业钴钼耐硫变换催化剂．     

浅析耐硫变换工艺运行的影响因素

分剐从预硫化效果、反硫化、工艺条件、催化剂中毒等方面分析了导致Co—Mo系耐硫变换催化剂活性降低的原因，浅析了影响催化剂活性及寿命的因素，对耐硫变换工艺运行操作具有一定作用。     

Kinetic studies with a sulfur-tolerant water gas shift catalyst

Experimental measurements have demonstrated high water gas shift (WGS) activity for molybdenum sulfide-based catalyst in the presence of hydrogen sulfide. The defect structure of the catalyst, controlled by the sulfur activity in the gas phase, has a dominant effect on the reaction rate. The reaction kinetics are interpreted in terms of Langmuir-Hinshelwood surface reaction. The mechanism is shown to involve a redox cycle with Mo(V) as an important species in WGS catalysis. XPS measurements provide information on the reductive sulfidation of the catalysts from the Mo(VI)-oxide state.     

Effect of the electronic properties of Mo sulfide phase on the hydrotreating activity of catalysts supported on Al2O3, Nb2O5 and Nb2O5/Al2O3

Activity in thiophene hydrodesulfurization (HDS) and in the three routes of 2,6-dimethylaniline (DMA) decomposition was examined on Mo sulfide catalysts supported on Al₂O₃, Nb₂O₅ and Nb₂O₅–Al₂O₃. Catalysts activity is enhanced when Mo phase is deposited on niobium-containing support. For HDS and for the hydrogenation route of DMA decomposition, the niobium-containing support strongly contributes to the catalyst activity whereas the activity of the Mo phase per Mo atom decreases with the increase of niobium amount in the support. By contrast, as for the DMA route, which leads to xylene formation (XYL), the activity of the Mo sulfide phase per Mo atom is strongly enhanced. The electronic properties of the MoS₂ phase were studied by means of IR spectroscopy of CO adsorption. Comparison of ν(CO/Mo) wavenumbers reveals an upward shift when Mo sulfide phase is deposited on Nb-containing support. The modification of the electronic properties of the sulfide phase is related to an interaction Mo–Nb either through the formation of a mixed Mo–Nb sulfide phase, or through the interaction MoS₂ slabs – support whose strength depends on the support acidity. Hence, the beneficial effect for xylene formation route is attributed to a decrease of the electron density of the Mo sulfide phase that should strengthen the DMA adsorption on the sulfide phase.     

新型全低变耐硫变换催化剂的研制

介绍了一种新型全低变催化剂的研究情况。该催化剂使用了特殊的三元载体,主要以Co-Mo-M1-M2等多元金属为活性组分。试验结果表明,该类催化剂具有良好的活性和耐热性能。     

铁系变换催化剂中助剂CoO作用的研究

运用X-射线衍射(XRD)。催化剂活性评价技术以及Mssbouer谱等手段研究了CoO在铁系催化剂中的作用。结果表明,CoO对铁系催化剂既有稳定催化剂结构的作用,又能使催化剂的活性大大提高。实验证明,使用CoO作为助剂可以起到显著的助催化作用。     

Cumene hydrocracking and thiophene HDS on niobia-supported Ni, Mo and Ni–Mo catalysts

Results are reported on the XPS characterization and catalytic activity in cumene hydrocracking (2.8 MPa, 623 K) and thiophene HDS (2.8 MPa, 523–573 K) of sulfided Ni, Mo and Ni–Mo catalysts supported on alumina and on pure and phosphated niobia. From the XPS results, evidence was obtained for the formation of a surface niobium sulfide with stoichiometry close to NbS₂ during catalyst sulfidation. Sintering of supported nickel during sulfidation occurred to a much smaller extent with the niobia-supported catalysts than with the alumina-supported ones. The dispersion of alumina-supported molybdenum was little influenced by sulfidation, whereas, with the niobia supports, the molybdenum surface concentration increased with sulfidation. With the alumina support, the Ni–Mo combination caused the dispersion of the sulfided nickel to be improved, possibly due to formation of a NiMoS phase. This was not observed with the niobia-supported catalysts.

Reasonable linear correlations were also found between the intrinsic activity for cumene hydrocracking and the amount of sulfided niobium in the catalysts, but the catalysts supported on phosphated niobia had a higher intrinsic activity than the ones supported on pure niobia. In thiophene HDS, the activity of the niobia-supported nickel catalysts was much larger than the activity of the alumina-supported ones. The activity of the niobia-supported molybdenum catalysts was smaller than that of the alumina-supported catalyst. With the bimetallic catalysts, little or no synergy was observed with the niobia-supported catalysts, in sharp contrast with the alumina case.     

铁系无铬NBC—1型高（中）温CO变换催化剂的工业试验研究

内蒙古工业化学工程系研制生产的铁系无铬ＮＢＣ－１型高温ＣＯ变换催化剂，经化肥厂整炉装填应用，并了该催化剂升温还原及两种工况的操作情况，证明了ＮＢＣ－１型催化剂具有易还原，低温活性好，蒸汽消耗低，ＣＯ转化率高，变换炉阻力小等特点，更重要的是彻底根尖了Ｆｅ－Ｃｒ系催化剂中铬组从对生产和使用人员的毒害及环境的污染。     

QDB-04型一氧化碳耐硫变换催化剂在德士古水煤浆气化制甲醇装置上的应用

总结了新型一氧化碳耐硫变换催化剂QDB-04在德士古水煤浆气化制甲醇装置上的首次工业应用情况。结果表明,该催化剂具有强度高、强度稳定性好、起活温度低、活性稳定性好、抗工况波动能力强等优点,能适应较高汽气比、较高一氧化碳含量和较高压力的工况条件。     

On the formation of cobalt–molybdenum sulfides in silica‐supported hydrotreating model catalysts

Model catalysts, consisting of a conducting substrate with a thin SiO₂ layer on top of which the active catalytic phase is deposited by spincoating impregnation, were applied to study the formation of the active CoMoS phase in HDS catalysts. The catalysts thus prepared showed representative activity in the hydrodesulfurization of thiophene, confirming that these models of HDS catalysts are realistic. Combination of the sulfidation behaviour of Co and Mo studied by XPS and activity measurements shows that the key in the formation of the CoMoS phase is the retardation of the sulfidation of Co. Complexing Co to nitrilotriacetic acid complexes retarded the Co sulfidation, resulting in the most active catalyst. Due to the retardation of Co in these catalysts, the sulfidation of Mo precedes that of Co, thereby creating the ideal conditions for CoMoS formation. In the CoMo catalyst without NTA the sulfidation of Co is also retarded due to a Co–Mo interaction. However, the sulfidation of Mo still lags behind that of Co, resulting in less active phase and a lower activity in thiophene HDS. This revised version was published online in June 2006 with corrections to the Cover Date.     

从CO变换工艺技术的历史演变看等温变换的历史性贡献

介绍了CO变换工艺技术和CO变换催化剂的历史演变,并从变换反应的物化基础提出变换工艺的发展和改进方向。介绍了CO变换工艺存在的新问题以及需要研究和解决的问题,阐述了CO等温变换工艺是对变换工艺的历史性贡献。