AATO馏分加氢裂化制取BTX的催化剂研究

采用高压加氢裂化装置对以不同分子筛为载体负载了镍金属的A、B、C型3种催化剂进行评价.结果表明,C型催化剂的比表面积和微孔孔容最大,AATO馏分的转化率为39.4％,苯和二甲苯的收率之和为18.5％.对加氢裂化性能较理想的C型催化剂添加钴金属进行性能改善,结果显示金属钴的添加有利于BTX收率的提高,BTX收率为25.9...     

加氢裂化组合催化剂的工业应用

介绍了加氢裂化FC-16//3976/FC-12组合催化剂在辽阳石化公司炼油厂160万t/a加氢裂化装置的工业应用情况。运转结果表明,加氢裂化FC-16/3976/FC-12组合催化剂级配使用具有较高的活性和选择性,在主要目的产品重石脑油收率满足需要的同时,柴油产率比上周期提高6%（质量分数）以上,干气和液化气产率明显降低,氢耗较低,达到了预期目的。     

用油溶性催化剂加氢裂化孤岛减压渣油的研究

介绍了抚顺石油化工研究院开发的油溶性金属催化剂。并以孤岛减压渣油为原料，采用该催化剂在高压釜上进行悬浮床加氢裂化反应试验，馏分油（<538 ℃）收率可达到70％以上。试验结果表明，油溶性金属催化剂具有较高的加氢活性和抑焦性能。     

低温费托合成蜡油加氢裂化精制技术的研究进展

低温费托合成技术因具有产品质量性好、反应耗能低、生产能力大且催化剂种类广泛等优点在煤化工领域备受关注,低温费托合成的蜡油产品可通过加氢裂化精制获取高品质清洁油品,具有巨大的应用价值。本文首先阐述了费托合成的产物特性,分析了加氢裂化过程的反应特点、双功能催化剂的碳正离子反应机理及蜡油主要反应历程。在此基础上,着重综述了蜡油加氢裂化双功能催化剂的研究进展,讨论了活性金属组分、载体以及助剂对加氢裂化过程的影响,分析表明活性金属的负载量、载体的酸量和孔道结构对催化性能有极大影响,合理优化和平衡加氢金属活性位和裂解酸性位是确保蜡油加氢裂化催化剂活性的关键。更为重要的是,基于分子筛载体的择形效应,实现载体多级孔结构和活性位的理性集成无疑会促进蜡油加氢产物的合理分布。     

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。     

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。     

NAS (novel aluminosilicates) as catalysts for the aromatisation of propane: Studies of zinc and gallium modified zeolite-based systems having various extents of XRD crystallinity

A review of existing literature on the behaviour of H-, Zn- and Ga-ZSM-5 systems in the aromatisation of propane suggest that no clear picture emerges regarding: (i) the relative merits of zinc and gallium with respect to activity and aromatics selectivity; (ii) the effects of the extent of crystallinity of the zeolitic material on catalysis. The work now reported involves a direct comparative study of H-NAS, Zn-NAS and Ga-NAS catalysts (NAS=novel aluminosilicates, comprising ZSM-5-based structures having XRD crystallinities ranging from the substantially amorphous to the partially crystalline and their highly crystalline ZSM-5 analogues. Zinc or gallium has been introduced into the parent zeolitic structure by means of solid-state ion-exchange. Zinc appears to enhance both activity and BTX (benzene, toluene and xylenes) selectivity, relative to the zeolitic parent solid, in contrast to gallium, which affects only BTX selectivity. In addition, optimum activity plus BTX selectivity under the conditions used are found for XRD crystallinities in the range 50–85%. The maximum BTX yields (single pass basis) are lowest for the H-NAS samples, markedly higher for the Zn-NAS catalysts, and at an intermediate level for the Ga-NAS samples.     

煤焦油加氢转化技术

分析了国内已经研究开发的煤焦油加氢转化技术,按照各技术的特点和轻油产品收率将现有煤焦油加氢转化技术划分为轻馏分油固定床加氢精制、减压馏分油固定床加氢裂化、全馏分油固定床加氢裂化、延迟焦化-固定床加氢裂化联合加工、悬浮床和沸腾床加氢裂化5类技术,分别介绍了每种技术的工艺流程特点和发展状况,分析了各自的优缺点、局限性、技术难点和实用性。建议今后应关注煤焦油生产芳烃产品、酚类产品技术的开发,以及开发煤焦油脱水脱盐技术,进一步完善、配套煤焦油加氢转化技术。     

加氢裂化催化剂研究进展

加氢裂化技术具有使原料油轻质化和直接生产清洁燃料及优质化工原料功能的工艺技术,是炼油工业中的绿色环保技术。随着全球石油趋向重质化、劣质化、环保法规日益严格、石油产品需求结构发生改变和中间馏分油需求的增加,促使对加氢裂化技术开发的深入。加氢裂化催化剂是加氢裂化技术的核心。我国现已拥有化工原料型、中间馏分油、尾油型和无定形催化剂的生产技术,UOP公司在加氢裂化段主要开发了灵活型、多产石脑油型以及多产中间馏分油型3大类催化剂;Chevron公司是最早开发加氢裂化技术的公司,开发了非贵金属无定形、非贵金属分子筛和贵金属分子筛3大类加氢裂化催化剂;Albemarle公司开发了KF-860加氢裂化预处理催化剂;Criterion公司开发了新型氧化铝载体,重点调节活性金属与载体之间的作用力,开发了新一代加氢预精制催化剂DN-3630。在新一代催化剂研发中,注重对微孔分子筛的开发和改性,使研制的催化剂具有很好的活性和稳定性等综合性能,由于微孔分子筛和介孔分子筛在酸性和孔结构上达到互补,随着介孔分子筛和微孔分子筛的相结合,微孔-介孔复合材料给加氢裂化催化剂的研发带来了新的发展机遇。     

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。     

Hydrocracking of Vacuum Gasoil on NiMoW/AAS-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Trimetallic Catalysts: Effect of the W : Mo Ratio

The effect of the W: (W + Mo) atomic ratio in NiMoW trimetallic catalysts on their catalytic and physicochemical properties is studied. The catalysts are prepared by impregnating a carrier containing amorphous aluminosilicate (AAS) and aluminium oxide with an aqueous solution containing Ni, Mo, W compounds, and citric acid. They are studied via XRF, TEM, NH₃ TPD, and low-temperature nitrogen adsorption and are tested in the hydrocracking of vacuum gasoil (VGO). The average length of a sulfide active component layer shrinks as the amount of Mo increases and the amount of W in the catalyst is reduced. XPS data indicate that the degree of sulfidation of tungsten in NiMoW trimetallic catalysts is lower than in NiW catalyst. Testing of the catalysts in hydrocracking of a straight-line VGO at 390–420°C, 16 MPa, a feedstock hourly space velocity (FHSV) of 0.71 h^?1, and a H₂: VGO ratio of 1200 L/L shows the activities of hydrodesulfurization, hydrodenitrogenation, hydrogenation, and hydrocracking grow along with the W: (W + Mo) ratio. When the process pressure is high and the amount of sulfur in the NiW feedstock is low, the catalysts have higher activity in the target reactions of VGO hydrocracking than NiMo catalyst.     

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.     

共胶法系列加氢裂化催化剂生产工艺的开发及工业应用

本文概述了共胶法系列加氢裂化催化剂生产工艺的技术特点，介绍了共胶法系列加氢裂化催化剂工业生产和应用情况。业已表明该系列催化剂易于大规模工业生产，催化剂具有很高的抗氮中毒能力、良好的产品选择性和加氢裂化活性稳定性，工业推广应用前景良好。     

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.     

分子筛重整催化剂研究进展

催化重整是芳烃的主要来源,但目前所用的重整催化剂存在对直链烷烃选择性差、生产过程中需不断补氯的缺点,国内外纷纷转向分子筛重整催化剂的研究。本文概述了国内外ZSM-5重整催化剂、载铂丝光沸石、β沸石以及L型分子筛重整催化剂的研究进展,详细分析了各种分子筛重整催化剂的优缺点。着重对ZSM-5和L型分子筛重整催化剂的反应性能和芳构化反应机理进行了系统概述,并对分子筛重整催化剂的发展趋势进行了探讨。指出分子筛重整催化剂代替传统重整催化剂是重整领域发展的必然趋势,结合失活机理对分子筛进行合理改性,提高催化剂的稳定性是分子筛重整催化剂发展的关键。另外,还应开发新型分子筛用于重整催化剂中,从而加快分子筛重整催化剂的工业化进程。     

环境友好型沸石催化剂的应用新进展

综述石油炼制和石油化工中的沸石新催化工艺，介绍了新工艺中改进的X，Y型，USY和ZSM-5沸石催化剂，以及新类型的SAPO，β沸石和MCM-22等；并概述了沸石催化在烟草工业中的应用。     

F-T合成蜡油加氢裂解反应过程研究进展

通过F-T合成生产液体燃料是转化利用煤、天然气和生物质并解决石油短缺问题的一种有效途径,采用轻度加氢裂解F-T合成过程中产生的高沸点蜡油可以生产清洁优质的柴油和喷气燃料。本文对近年F-T合成蜡油加氢裂解的研究进展进行了综述,简要介绍了F-T合成蜡油加氢裂解的反应机理,讨论了集总动力学和单事件动力学在F-T合成蜡油加氢裂解中的应用情况,对F-T合成蜡加氢裂解催化剂体系以及反应影响因素进行了分析。反应精馏工艺可以提高F-T合成蜡加氢裂解高转化率时柴油的选择性,除了开发更高效的催化剂以外,F-T合成蜡油加氢裂解反应精馏的研究与应用将具有重大前景。     

A comparative activity study of a new ultra-dispersed catalyst system for a hydrocracking/hydrotreating technology using vacuum residue oil: Merey/Mesa

Ultra-dispersed catalysts give an improvement over the main reactions activity by having a low deactivation rate. They provide as well other advantages like a diminution in the catalysts metal concentration, a reduction in contaminants and also these catalysts can be used in almost every area where heterogeneous catalysts are used. Catalysts synthesis optimization is important to improve process recovery, especially in hydrocracking/hydrotreating processes, where feedstock is vacuum residue. Here, we have evaluated the catalytic performance of two molybdenum–nickel catalysts prepared using different emulsion formulation, named E-T (base catalyst) and AT-48 (new catalyst). Our results showed that, the percentage of converted products for VR 500 °C⁺, asphaltenes and microcarbon are comparable for both E-T and AT-48 catalysts, despite the fact that for the latter a lower molybdenum concentration was used. In addition, post-catalytic particles analyses using SEM and TEM techniques demonstrated that AT-48 catalyst showed a non-aggregated and homogeneous narrower distribution of metallic particles than E-T one. The lower average particle size distribution is related to the improvement of the liquid product yields for the hydroconversion of Mery/Mesa VR using the AT-48 catalyst.     

Research and development of hydrocracking catalysts and technologies in China

Hydrocracking of petroleum feedstock represents a compelling route for the production of industrial clean fuels, which has triggered the continuous research and development of core technology related areas such as catalysts, reaction engineering and engineering design. This review particularly focuses on the research and development of catalysts and catalytic processes for hydrocracking of petroleum feedstock in China. Hydroprocessing technologies of China keep pace with the up-to-date progress of the world, and some of the technologies have achieved leading role in the world. It is noted that China Petroleum and Chemical Corporation has a full range of hydroprocessing technologies and provides corresponding “tailor-made” catalysts. Through the efforts of several generations, 20 categories of the catalysts including more than 60 brands have been developed, among which more than 40 brands have been successfully applied for more than 130 times. Importantly, the pivotal technical improvements including the deep drawing vacuum gas-oil (VGO) and de-asphalting oil hydrocracking technology to improve material adaptability, the high value-added hydrogenation technology to convert high aromatic diesel conversion to naphtha, the hydrocracking technology using VGO-catalytic diesel blends, the Fushun Research Institute of Petroleum and Petrochemicals’ diesel to gasoline and diesel hydrocracking technologies, and the Sheer hydrocracking technology to reduce energy are reviewed.     

Hydrocracking of Fischer‐Tropsch Wax with Tungstovanadophosphoric Salts as Catalysts

The synthesis of liquid hydrocarbons from CO₂ and H₂, based on renewable energy and H₂O electrolysis, respectively, in a power‐to‐liquid process is a promising concept for the substitution of fossil fuels. Such a process is based on Fischer‐Tropsch synthesis followed by hydrocracking to convert waxy products into transportation fuels such as gasoline and diesel oil. Heteropolyacid cesium salts as catalysts show appropriate activity for hydrocracking, and the selectivity in cracking model hydrocarbons and Fischer‐Tropsch wax can be tuned by the vanadium content of the catalyst. Thermal stability and surface properties were investigated, and the catalysts are compared with a classical H‐Y‐type zeolite used for hydrocracking.