浆态床重油加氢裂化油溶性催化剂的研究进展

油溶性催化剂分散性好,加氢抑制结焦性能高,在浆态床重油加氢工艺中将具有良好的工业应用前景。围绕着近年来浆态床重油加氢裂化油溶性催化剂的研究进展,重点阐述了单金属油溶性催化剂、混合油溶性催化剂和多金属油溶性催化剂的研究现状,并展望了油溶性催化剂的发展前景。     

浆态床渣油加氢油溶性催化剂研究进展

介绍了近年来浆态床加氢裂化处理渣油工艺中油溶性分散催化剂的研究进展,阐述了油溶性单金属催化剂和油溶性双金属催化剂的研究现状,并展望了油溶性催化剂应用于浆态床渣油加氢裂化工艺的发展前景.     

油溶性铁镍催化剂在煤/重油加氢共炼中的应用

以褐煤A为原料煤,以马瑞常压渣油为原料油,采用实验室合成的油溶性铁镍复合催化剂在高压釜中模拟煤/重油浆态床加氢共炼反应进行活性评价.采用XRD,SEM和TEM等表征手段分析催化剂的硫化产物及煤/重油加氢共炼体系产生的固体残渣,探究该复合催化剂与单金属催化剂之间产生活性差异的原因.结果表明:相比于油溶性单金属铁、油溶性单金属镍催化剂,油溶性铁镍复合催化剂具有更高的干基无灰煤转化率,可达87.37%.油溶性铁镍复合催化剂的硫化产物结晶度低,颗粒表面粗糙,分散度高,不仅存在铁、镍的单金属硫化物,而且形成了铁镍混晶的硫化物(Fe-Ni-S混晶).油溶性铁镍复合催化剂作用下得到的固体残渣,粒径小,结构松散,芳香度低,进一步证实油溶性铁镍复合催化剂促进了煤的深度转化.     

渣油加氢裂化反应中油溶性催化剂的抑焦性能

以辽河常压渣油为研究对象,通过高压釜模拟渣油加氢裂化反应,对不同油溶性催化剂体系反应后的生焦量、生焦状况及产物进行分析,深入研究渣油加氢裂化反应中油溶性催化剂的抑焦性能.研究表明,随着活性金属含量的增大,油溶性单金属Co催化剂和Ni催化剂的生焦量减少,Co - Fe或Ni - Fe复配体系具有协同效应,抑焦性能增强,由...     

FCC金属钝化剂的制备研究进展

从制备方法、使用性能以及理化性质3个方面综合论述了国内外金属钝化剂研究的进展情况,重点讨论了金属钝化剂的制备方法,金属钝化剂可以抑制镍和钒等金属对催化裂化催化剂的污染,使被污染催化剂的性质得到改善,水溶性金属钝化剂比油溶性金属钝化剂具有更多的优点,采用非锑基金属钝化剂代替有毒的锑基金属钝化剂将是未来的发展方向。     

催化剂撇头和压降超高原因分析

对固定床反应器催化剂进行撇头是对床层压降超高后有效的处理措施,影响催化剂床层压上升的原因有原料保护、油溶性金属、原料杂质、操作波动等多个因素,生产运行中必须有针对性的实施管理,才能有效的抑制催化剂床层压降的快速上升。     

浆态床油溶性加氢催化剂前体的研究进展

浆态床渣油加氢工艺是加工劣质油品的有效方法,由于原料具有高沥青质、高金属含量的特点,工艺的核心在于提供稳定高效的加氢裂化催化剂。油溶性催化剂前体能够原位转化为纳米级尺寸的催化剂活性相,其分散度高、加氢活性高,因而成为浆态床渣油加氢工艺的首选。本文主要介绍了4类常见的油溶性有机钼化合物,即二烷基(芳基)二硫代氨基甲酸钼(Mo-DTC)和二烷基二硫代磷酸钼（Mo-DTP）、环烷酸钼（MoNaph）、异辛酸钼、六羰基钼,比较它们在氢气和硫作用下的转化过程以及对重质原料的加氢性能,找出各自在应用过程中的优缺点,为深入研究和设计开发油溶性催化剂前体提供思路和借鉴。     

稠油水热裂解油溶性催化剂性能研究

合成的油溶性钴系和镍系催化剂作为稠油水热裂解反应的催化剂,具有良好的热稳定性,与表面活性剂石油磺酸盐和供氢剂甲苯复配,降粘重复性稳定。实验结果表明,反应温度180 ℃,油溶性催化剂体系投药量质量分数为0.4%时,可使中国石油辽河油田稠油降粘90%以上;现场试验表明,该催化剂体系有效降低稠油粘度,实验初期稠油的降粘率大于74%。     

油溶性纳米MoS2加氢催化剂的合成、表征和应用

传统MoS₂加氢催化剂粒径大、油溶性差而催化效率相对较低。纳米粒子合成方法很多，其中液相化学合成技术尤其水(溶剂)热、微乳液、单层二硫化钼重堆积和微波液相介电加热法等更为便捷、高效。在油溶性纳米MoS₂的合成中，表面修饰剂的选择最为关键。综述了油溶性纳米MoS₂的合成、表征和应用研究进展，提出了高稳定性、高活性和油溶性纳米MoS₂加氢催化剂高效合成优化参数，为实现工业应用提供了参考。     

聚醚润滑基础油(PAG)的实验室研究

以环氧化合物为原料，单元醇为起始剂，碱金属作为催化剂聚合制得油溶性聚醚润滑基础油。考察了不同碱金属催化剂、催化剂浓度、聚合温度等条件对聚醚合成润滑基础油收率的影响。通过实验得出最佳催化剂为氢氧化钾，反应温度为130℃,催化剂用量为0.6%。并通过凝胶渗透色谱(GPC)、红外光谱(IR)和质谱(MS)对其进行表征。结果表明KOH催化剂在催化目标相对分子质量较大的聚醚时产物收率较低，并确定了聚醚结构的存在，验证了环氧化合物制备油溶性聚醚的可行性。     

渣油悬浮床加氢裂化催化剂研究

介绍了开发的水溶性和油性渣油悬浮床加氢裂化催化剂,并采用该催化剂进行加氢裂化实验。以常、减压渣油为原料,单程通过时<538　℃的馏分油收率为60％～90%,反应生成油的甲苯不溶物质量分数可以控制在1.0%以下。在催化剂开发的过程中,采用“均匀设计”软件进行实验方案的设计并对试验结果进行优化,所开发的催化剂具有较好的加氢和抑焦性能     

渣油悬浮床加氢裂化技术的初步研究

本文介绍了抚顺石油化工研究院开发的渣油悬浮床加氢裂化工艺及催化剂，采用该催化剂加氢处理常、减压渣油，单程通过得到馏分油（<500℃）的收率达到70%以上。并在200ml小型装置上进行了500h连续运转。采用尾油循环和其它组合工艺，可得到较高的渣油加氢转化率。     

炼油催化剂技术的新进展

综述了炼油领域催化剂的新进展,包括催化裂化、催化重整、柴油和汽油加氢脱硫、渣油加氢、异构化、烷基化和加氢裂化。     

Metal-ion pillared clays as hydrocracking catalysts (II): effect of contact time on products from coal extracts and petroleum distillation residues

Novel catalysts have been prepared, based on montmorillonite (a natural clay) and laponite (a synthetic clay) pillared with tin, chromium and aluminium pillars as well as layered double hydroxides based on polyoxo-vanadate and -molybdate as previously described. These novel catalysts were compared initially with a standard Ni/Mo catalyst supported on alumina and a dispersed catalyst, Mo(CO)₆ in hydrocracking a coal extract for a short contact time of 10 min at 440 °C in a microbomb reactor with tetralin solvent and hydrogen at a pressure of 190 bar. In the present work, the best of the novel catalysts, chromium montmorillonite calcined at 500 °C and tin laponite, have been compared with the supported catalyst and a dispersed catalyst (Mo(CO)₆) in the repeated hydrocracking of fresh coal extract over three sequential periods of 1 h. Also, the chromium montmorillonite calcined at 500 °C has been used in the hydrocracking of primary coal extracts, prepared in the flowing solvent liquefaction rig from Pittsburgh #8 and Illinois #6 coals, for reaction times of 10 min and 2 h. Further, the chromium montmorillonite calcined at 500 °C and tin laponite, have been compared with the supported catalyst and in the absence of a catalyst, in the hydrocracking of a petroleum distillation residue with 10 min and 2 h reaction times. Results were compared by size exclusion chromatography in NMP solvent and by UV-fluorescence and evaluated by the extent of the shift of the SEC profile to small molecules and by the shift of the synchronous UV-fluorescence profiles to shorter wavelengths. The performances of both catalysts at short, long or repeated reaction times are seen to be better than that of the conventional NiMo catalyst for the hydrocracking of coal-derived materials and a petroleum residue. Trials on a longer time scale are necessary in the next level of evaluation.     

面向21世纪的炼油催化技术的新进展(续完)

本文系22篇有关炼油催化技术最新文献述评, 它涉及异构化、烷基化以及重整油改质与脱苯用催化剂, 馏份油的加氢处理与加氢裂化, 流化催化裂化渣油流化催化裂化和增产烯烃的流化催化裂化工艺, 渣油加氢处理以及生物催化脱硫。     

Industrielle Anwendung von zeolithischen Katalysatoren beim Hydrocracken

Industrial application of zeolitic catalysts in hydrocracking . For maximum production of gasoline by hydrocracking using zeolite type catalysts two cracking schemes are presented and the operation conditions, feedstocks, yields, and material balances are discussed. The advantages of zeolitic hydrocracking catalysts are outlined. The main catalyst parameters controlling activity and selectivity are described and a scheme for the preparation of zeolitic catalysts is given, which illustrates the superiority of zeolitic hydrocracking catalysts over amorphous ones. Finally, the hydrocracking of residues is reviewed and a typical process together with the product characteristics and yields obtained is described.     

加氢裂化催化剂失活与再生

利用XRD、XPS、TPR、ICP、IR、TEM 等技术, 测试和表征几种不同类型新鲜的、失活的和再生后工业用非贵金属加氢裂化催化剂的性能, 找出该催化剂失活的主要原因。经研究发现,加氢裂化预精制催化剂主要失活原因是积炭和金属聚集; 加氢裂化催化剂主要失活原因是积碳、所含沸石倒塌、金属聚集、孔结构堵塞及倒塌, 对于单段加氢裂化催化剂失活原因, 还包括酸中心中毒等。本文还探讨了器内与器外再生方式利弊及今后发展趋势。     

Hydrocracking Brazilian Marlim vacuum residue with natural limonite. Part 1: catalytic activity of natural limonite

An experimental study examined the catalytic effects of natural Australian (AL) and Brazilian (BL) limonites used in hydrocracking Brazilian Marlim vacuum residue (ML-VR). The catalytic behavior of the limonites was compared with a conventional NiO-MoO₃-Al₂O₃ (NiMo) catalyst. Diphenylmethane (DPM) and 1-methylnaphthalene (1-MN) were used as standards. The order in which coke and gas formation were suppressed during hydrocracking of ML-VR was NiMo>BL>AL, which is the same order as for the hydrogenation activity observed with the standard compounds. By contrast, the limonite catalysts exhibited relatively higher conversions and distillate yields in ML-VR hydrocracking than did the NiMo catalyst with the order of conversion and distillate yield (yield of the fraction with boiling point of 540 °C) being AL>BL>NiMo, which is the same order obtained for catalytic cracking of the two standards. Coke formation was effectively suppressed at high hydrogen pressures. The limonite catalysts showed lower activities for nitrogen and sulfur removal than did NiMo, but both proved to have a larger activity for nickel removal.     

加氢裂化FC-16和FC-14催化剂组合工艺应用研究

FC-16和FC-14两种加氢裂化催化剂组合工艺在1.0Mt/a加氢裂化装置首次工业应用,取得了较好的效果。从实际生产数据入手,根据FC-16和FC-14两种分子筛型和无定形催化剂特性,重点研究了催化剂活性、选择性、稳定性,以及两种催化剂的性能匹配情况。另外工业应用还表明两种类型加氢裂化催化剂组合工艺可以明显降低装置能耗,提高装置运行的安全性。