钼/活性炭渣油加氢催化剂的制备

渣油加氢工艺是一种渣油深度加工技术,高性能渣油加氢催化剂的研发是其核心。本文以钼酸铵为活性组分前体,采用等体积法制备了钼/活性炭催化剂（Mo/AC）,考察了制备条件如金属负载量、焙烧温度、溶液pH值等对催化剂的影响,利用XRD、SEM、XPS等手段对催化剂进行了表征。在浸渍时间4h,焙烧温度440 ℃条件下制备出负载量8%（以MoO3 计）的Mo/AC 催化剂,活性组分钼呈高度分散的单层分布,催化剂活性评价结果表明,渣油转化率可达79%,馏分油收率为75%,同时,生焦率控制在1.5%的较低水平上。     

活性炭负载型加氢催化剂研究

介绍了钯－炭加氢催化剂的制备方法,并讨论了活性炭表面的物化性质对催化剂性能的影响。     

活性炭负载型加氢催化剂研究

介绍了钯－炭加氢催化剂的制备方法,并讨论了活性炭表面的物化性质对催化剂性能的影响。     

新一代高性能渣油加氢催化剂的工业应用

随着原油劣质化趋势的加剧及环保法规的日益严格,渣油加氢技术已成为炼厂提高轻油收率的关键技术,而催化剂是渣油加氢技术的核心。主要介绍了新一代高性能渣油加氢催化剂在中国石油四川石化300万t/a渣油加氢脱硫装置的应用情况。     

渣油加氢催化剂的研究和应用

渣油加氢处理技术是近年发展最快的技术领域。渣油加氢处理催化剂是此技术的关键。多种固定床渣油加氢处理催化剂在国外已进行了开发和工业应用。我国也开发了多种固定床渣油加氢处理催化剂，实践表明这种催化剂具有良好的活性和稳定性，产品质量良好，收率高，可为RFCC提供优质的原料。悬浮床渣油加氢处理催化剂也在开发之中，中试试验取得了良好的结果。     

统计方法在渣油加氢催化剂生产中的应用

统计技术是研究事物变异性及其规律的方法。在催化剂的生产过程中，通过分析检测，应用统计技术来优化工艺参数，实现产品的质量控制。本文介绍了相关及回归分析和质量控制图在渣油加氢催化剂担体成型过程中质量控制上的应用。     

新型渣油加氢脱硫催化剂的研究

本文介绍了新型渣油加氢脱硫催化剂及其制备方法, 制备的关键是采用独特的载体制备技术和选用合适的助剂。考察了不同金属配比对催化剂活性的影响。     

渣油加氢催化剂反应动力学的研究进展

介绍了渣油加氢催化剂反应动力学的研究进展,列举了几类渣油加氢催化剂反应动力学模型。利用这些模型可以预测催化剂使用周期,帮助设计催化剂级配方案,并有助于对渣油加氢反应过程进行深入研究。     

渣油加氢处理催化剂积炭分析

采用热重、差热分析、低温氮吸附、元素分析等技术对渣油加氢处理过程中5种催化剂上的积炭进行了分析.结果表明,结焦催化剂表面积炭沉积和孔道堵塞现象严重,比表面积和孔容大量损失,孔分布向小孔范围迁移,催化剂孔径越小,损失越严重.催化剂上沉积的焦炭可分为低温型和高温型两种,前者燃烧放热集中在400℃左右,后者集中在470℃左右.积炭形成类型与积炭前身物--沥青质的结构有关,芳香碳分率低,缩合指数小的沥青质形成低温型积炭;芳香碳分率高,缩合指数大的沥青质形成高温型积炭.催化剂促使沉积物脱氢形成积炭,并且使积炭从低温型向高温型转化,催化剂活性越高,转化越明显.     

钼/活性炭渣油加氢催化剂的硫化

钼/活性炭催化剂是一种新型渣油加氢催化剂,其硫化效果直接决定着催化剂的活性和稳定性。实验考察了硫化条件对钼/活性炭催化剂（Mo/AC）硫化度的影响,运用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）和透射电镜（TEM）等手段对硫化态催化剂进行了表征。结果表明,以二硫化碳为硫化剂,正十六烷为硫化介质,在硫化温度350 ℃,硫化时间3 h,氢气初压6 MPa条件下催化剂硫化度为85%,活性相MoS2堆垛结构为4～6层,晶片长度为6～10 nm,分布比较均匀,具有良好的加氢活性。     

圆柱状成形Ru/AC氨合成催化剂制备及性能

将水洗处理的椰壳活性炭研磨至小于0.08 mm,加入粘合剂挤压成长度3～10 mm、3～5 mm的圆柱形,颗粒经120 ℃烘干、1 900 ℃高温处理和400 ℃经氧、氮等混合气处理后,作为Ru/AC催化剂载体。其侧压强度从无定形的40 N·cm^－1提高到成形后的91 N·cm^－1,磨耗率从无定形的5%左右降低到成形后的0.05%。以成形椰壳炭为载体的Ru/AC催化剂的活性与无定形活性炭为载体时相当,具有在低温、低压、低氢氮比和原料气高氨含量下高活性的特点,且具有很好的耐热性。与无定形椰壳炭相比,以成形椰壳炭为载体制备的Ru/AC氨合成催化剂更适合工业氨合成装置使用。     

Ni-Fe/C催化剂制备及其催化苯酐选择性加氢制苯酞

以NaBH4对疏水活性炭进行处理,采用等体积浸渍法制备疏水活性炭负载掺杂助剂Fe的Ni基催化剂,用于苯酐液相选择性加氢制苯酞,考察Ni含量和活性炭处理对催化剂性能的影响。结果表明,疏水活性炭经NaBH4处理后制备的15%Ni-Fe/C催化剂对苯酐加氢表现出很好的催化性能,在180 ℃、4.0 MPa、苯酐5.0 g、催化剂用量以Ni占原料质量的1%计和甲苯50 mL条件下,苯酐转化率为100%,苯酞选择性为95.2%,催化剂重复使用5次,仍保持很好的活性和选择性。     

Ni catalysts supported on activated carbon from petcoke and their activity for toluene hydrogenation

Petroleum coke (petcoke) is an abundant resource that can potentially be converted to catalyst support materials through activation to increase the surface area and reduce the sulphur content. In this work, potassium hydroxide (KOH) catalysed activation was employed with petcoke to produce activated carbons, which were characterised with nitrogen physisorption, X‐ray diffraction, scanning electron microscopy and temperature‐programmed reduction. With activation temperatures between 500 and 800°C, the surface area increased from 4 m²/g to between 200 and 2400 m²/g while the sulphur content was reduced from 6.6 wt% to between 1 and 0.2 wt%. Nickel catalysts (nominally 5 wt%) were prepared on the activated carbon supports using wet impregnation. The activities of these catalysts were measured for toluene hydrogenation in a plug‐flow reactor with a toluene liquid hourly space velocity of 2.4/h, a pressure of 1.38 MPa, and a H₂/toluene mole ratio of 90. The catalytic activity varied between zero for nickel supported on petcoke to 98% conversion, with essentially 100% to methylcyclohexane for nickel supported on carbon activated at 750°C. Thus, activated carbon from petcoke was a suitable support for Ni‐based catalysts when used for toluene hydrogenation as a model reaction. © 2011 Canadian Society for Chemical Engineering     

钌炭催化剂的制备及其在芳环加氢反应中的应用

芳环加氢反应是最重要的合成反应之一,钌炭催化剂在芳环加氢反应中具有优异的催化性能。综述钌炭催化剂的制备方法和载体性质对钌炭催化剂的影响以及钌炭催化剂在苯、苯甲酸和对苯二甲酸二甲酯等芳环加氢反应中的应用进展。负载型钌炭催化剂的制备方法主要有浸渍法、沉淀法和升华法,超声辅助浸渍法可将大部分钌纳米粒子引入到炭载体的孔道内部,得到限域型负载钌炭催化剂。而镶嵌式钌炭催化剂主要是指通过原位炭化的方法将钌粒子部分镶嵌在炭的孔壁上,一步得到钌炭催化剂,其制备方法主要有软模板剂法和硬模板剂法。除制备方法外,炭的骨架结构、表面性质及氮掺杂对钌炭催化剂的性能影响也较大。镶嵌式钌炭催化剂具有钌纳米粒子和炭载体之间的相互作用强、催化剂抗流失及烧结性能好,在芳环加氢反应中表现出卓越的催化性能和稳定性。随着新制备技术的出现,新型镶嵌式钌炭催化剂将可能实现产业化。     

Characterization of dispersed hydroprocessing catalysts prepared in reversed micelles

Fe, Co and Ni particles were prepared in water/polyoxyethylene-4-laurylether/n-hexane and water/polyoxyethylene-4-laurylether/decahydronaphthalene microemulsions by reduction of metal nitrates dissolved in the water pools of the reversed micelles. The particles were mostly monodispersed with average diameters in the range 8 to 23 nm, as determined by dynamic light scattering (DLS). However, significantly smaller size estimates were obtained using transmission electron microscopy (TEM). The average DLS particle diameters increased with increased average diameter of the reversed micelles, and the diameter of the reversed micelles increased with an increase in the microemulsion water: surfactant ratio and metal ion concentration. The diameter of the reversed micelles was also dependent upon the metal dissolved in the water pool, increasing in the order Ni < Co < Fe. These trends are explained in terms of changes that occur to the microemulsion hydrophilic-lipophilic balance. Preparation of nickel and cobalt sulfides by sulfidation of the metal salt with H₂S at low temperature, yielded much larger diameter particles (average diameter 75 nm). Measurement of the activity of the sulfided catalysts showed that the Co catalyst was more active than the Ni catalyst for the hydrocracking of diphenylmethane, and Co was more effective than Fe in reducing coke yield during Cold Lake residue hydroprocessing.     

Activity of hydroprocessing catalysts prepared by reprocessing spent catalysts

In this study, two spent catalysts from the 3rd and 4th fixed beds of the atmospheric residue desulfurization (ARDS) process and one spent catalyst from the H-Oil process employing the expanded bed were used as the starting material for preparation of hydroprocessing catalysts. The spent catalysts were used either in a coked or decoked form. The procedures involved pulverizing the spent catalysts before mixing, kneading and extruding with boehmite in the presence of peptizing agent such as HNO₃. The hydrodesufurization (HDS) and hydrodemetallization (HDM) activities of the new catalysts were evaluated in the microreactor using the atmospheric residue derived from Kuwait crude. The new catalysts prepared from the spent catalysts used in the fixed bed reactors exhibited higher activity than that of commercial catalysts. The HDS activity of the new catalysts prepared from spent catalysts used in the ebullated bed reactor was much lower than that of the other catalysts. This was attributed to a high content of vanadium in the former spent catalyst. At the same time, the adverse effect of vanadium on HDM was much less evident.     

废菌渣活性炭的制备及对废水中硝基苯的吸附

以废菌渣为原料制备活性炭,采用能量-色散光谱（EDS）和傅里叶变换红外光谱仪（FTIR）进行表征,结果表明：活性炭表面具有多种官能团,有利于提高对硝基苯的吸附。并研究了活性炭吸附硝基苯的影响因素（pH、初始浓度、吸附时间、投加量）、吸附等温线及热力学。结果表明：在常温中性pH条件下,初始浓度为50mg/L,活性炭用量为0.15g时硝基苯去除率可达98%,出水水质满足《污水综合排放标准》（GB 8978－1996）中对硝基苯浓度低于2.0mg/L的要求。活性炭对硝基苯的吸附具有较快的吸附速率,即1min接近平衡。该吸附行为是自发放热反应,可以用Freundlich模型很好地拟合。废菌渣活性炭对硝基苯的吸附主要是疏水作用和氧化钼活化共同作用的结果。因此,以农业废弃物-废菌渣制备得到的废菌渣活性炭具有良好的经济实用性,可用于废水处理中,实现以废治废的目的。     

活性炭负载催化剂臭氧催化氧化处理印染废水研究

以堇青石蜂窝陶瓷、硅藻土、活性氧化铝和活性炭作为载体、金属氧化物(FexOy、CuO、NiO、MnxOy、BaO)作为催化活性组分,对臭氧催化氧化印染废水进行了试验对比,并对影响载铁型活性炭催化剂臭氧催化氧化印染废水的因素进行了研究。结果表明,载铁型的催化剂活性相对较高,当焙烧温度为750℃时,催化性能最好。利用载铁型活性炭催化剂,在臭氧质量浓度为10mg/L、pH值为6、反应时间为60min的条件下,催化氧化具有最佳的效果,COD去除率达86%;催化剂的重复利用性好,连续使用12次,COD的去除率仍可达64%。