煤焦油加氢脱硫催化剂的研究进展

随着石油资源的日趋减少,煤焦油加工技术受到关注。汽车尾气中含有的硫化物严重污染环境,如何高效脱除煤焦油中含硫化合物的硫原子是开发煤焦油加氢脱硫催化剂的研究重点。简述煤焦油中含硫化合物的分布状况及其特点,并分别从贵金属、非贵金属、过渡金属磷化物、氮化物、碳化物及金基双金属催化剂方面综述煤焦油加氢脱硫催化剂的研究现状,针对煤焦油中含硫组分复杂多样的特性,提出研发高效和高活性煤焦油加氢脱硫催化剂的新方向。     

加氢脱氮催化剂及反应机理研究进展

介绍了各馏分油品中含氮化合物的分布规律和特点,概述了加氢脱氮反应过程中含氮化合物进行加氢和C-N键断裂的反应机理及典型含氮化合物的反应网络;总结了传统加氢脱氮催化剂及其载体的制备、改性和调变方法,论述了新型金属碳化物、氮化物、磷化物催化剂的结构特性及各类催化剂的加氢脱氮反应性能.关联了催化剂的物理化学性质对加氢脱氮反应的影响,提出了高活性加氢脱氮催化剂的研制思路和途径.     

低温煤焦油加氢催化剂的研究进展

以低温煤焦油中典型化合物的脱硫、脱氮反应路径为切入点,结合低温煤焦油催化剂的研究进展和现状,指出了低温煤焦油催化脱硫与脱氮存在内在联系,并展望了低温煤焦油加氢催化剂的研究方向。     

低温煤焦油加氢催化剂的研究进展

以低温煤焦油中典型化合物的脱硫、脱氮反应路径为切入点,结合低温煤焦油催化剂的研究进展和现状,指出了低温煤焦油催化脱硫与脱氮存在内在联系,并展望了低温煤焦油加氢催化剂的研究方向。     

加氢脱氮反应研究进展

介绍了油品加氢脱氮反应机理;详细综述了非杂环类化合物、碱性杂环化合物、非碱性杂环化合物等含氮化合物的加氢脱氮反应网络;还从活性组分、载体的改性、助剂的选择等加氢脱氮催化剂改性途径方面作了论述.     

煤焦油加氢精制催化剂研究进展

煤焦油加氢制取清洁油品是实现煤焦油高效转化的有效手段。随着我国对燃料油品标准的不断提高，对煤焦油进行加氢脱氮、加氢脱硫成为研究热点。本文主要介绍了煤焦油性质和煤焦油加氢工艺，重点综述了煤焦油加氢催化剂研究现状，并展望了煤焦油加氢催化剂的研究方向，指出开发新型绿色友好的加氢催化剂是实现煤焦油加氢技术的关键。     

加氢脱氮反应与加氢脱氮催化剂的研究进展

介绍石油馏分中主要含氮组分和其结构特性，以及典型含氮化合物的加氢脱氮反应网络、反应机理、反应动力学，阐述了加氢脱氮催化剂改性的不同途径：载体的改性、活性组分和助剂的选择、活化方法的改进等。     

中低温煤焦油加氢脱氮催化剂研究进展

详细介绍了煤焦油加氢技术,将现有煤焦油加氢转化技术划分为轻组分加氢,脱酚加氢,加氢裂化-加氢改质和全馏分加氢四种,分别介绍了每种技术的工艺流程特点和发展状况。阐述了国内外加氢催化剂研究进展,分析了催化剂中活性金属、载体和助剂的种类及对催化剂性能的影响;结合煤焦油加氢催化特点,展望了加氢脱氮催化剂的研究方向,旨在为煤焦油加氢催化剂研究提供一定的理论依据。     

煤基液体燃料加氢脱氮催化剂的研究动态

煤基粗油中氮含量高达4500mg/L左右,采用石油系的NiMoS催化剂很难实现含氮芳香族化合物的脱除。为开发针对性更强、更高效的加氢脱氮催化剂,本文对煤基粗油加氢脱氮的催化剂研究动态进行了综述。首先介绍了煤基粗油中含氮芳香族化合物的组成及特点,接着围绕传统硫化物催化剂和脱氮性能较高的贵金属催化剂,从活性相的构筑与调控、载体在催化剂中的作用等方面进行了分析,最后比较了上述两种催化剂的催化性能。结果表明：贵金属催化剂活性高于传统硫化物催化剂;添加助金属形成合金可提高贵金属耐硫性与稳定性;采用具有一定酸性、与活性中心相互作用适中的载体的催化剂脱氮性能更佳。在综合分析已有文献和工作基础上,得出只有依据反应体系、特定反应过程来设计专一的加氢脱氮催化剂,才能从根本上提高含氮化合物的脱除率。     

乙二醇对NiMoP/Al2O3催化剂上喹啉加氢脱氮反应的影响

燃料油中的含氮化合物是空气中NOx的主要来源,为了降低NOx排放,满足日益严格的排放标准,需要降低燃料油中含氮化合物含量,开发研制高效的加氢精制催化剂是达到这一目标的有效手段。通过在NiMoP浸渍液中添加不同含量乙二醇,制备一系列NiMoP/Al₂O₃催化剂,以喹啉为模型化合物,对催化剂进行加氢脱氮活性评价,分析表征各类脱氮产物。结果表明,乙二醇的加入能够大幅提高喹啉脱氮率,尤其是喹啉全加氢产物中C-N键的直接断键能力得到较大提高。     

Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions

Catalyst particle shapes and pore structure engineering are crucial for alleviating internal diffusion limitations in the hydrodesulfurization (HDS)/hydrodenitrogenation (HDN) of gas oil. The effects of catalyst particle shapes (sphere, cylinder, trilobe, and tetralobe) and pore structures (pore diameter and porosity) on HDS/HDN performance at the particle scale are investigated via mathematical modeling. The relationship between particle shape and effectiveness factor is first established, and the specific surface areas of different catalyst particles show a positive correlation with the average HDS/HDN reaction rates. The catalyst particle shapes primarily alter the average HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. An optimal average HDS/HDN reaction rate exists as the catalyst pore diameter and porosity increase, and this optimum value indicates a tradeoff between diffusion and reaction. In contrast to catalyst particle shapes, the catalyst pore diameter and the porosity of catalyst particles primarily alter the surface HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. This study provides insights into the engineering of catalyst particle shapes and pore structures for improving HDS/HDN catalyst particle efficiency.     

Hydrodenitrogenation of isoquinoline

To determine the formation and reactivity of addition compounds produced during hydrodenitrogenation (HDN), we investigated the HDN of isoquinoline for a sulfided Ni–Mo/Al₂O₃ catalyst operated under a hydrogen pressure of 12 MPa (cold charge) in the temperature range 300–375°C. The reaction products were classified into five groups of compounds:

1. hydrogenated derivatives of isoquinoline (tetrahydroisoquinolines, decahydroisoquinolines, and their isomers);

2. nitrogen-containing ring-opened products (1-amino-2-(2-methylphenyl)ethane and 1-amino-1-(2-ethylphenyl)methane);

3. denitrogenated products (1-ethyl-2-methylbenzene, 1-ethyl-2-methylcyclohexane, and their isomers);

4. addition products (hydrocarbons with molecular weights of 238, 244, and 250 and nitrogen-containing compounds with molecular weights of 249, 251, and 257); and

5. cracked products (toluene, ethylbenzene, dimethylbenzenes, and their hydrogenated derivatives).

Most of the nitrogen-containing addition compounds appear to be substituted on the nitrogen atom. The HDN of isoquinoline was more than 10 times faster than the HDN of quinoline, whereas the hydrogenation of isoquinoline was difficult compared to the hydrogenation of quinoline. The reaction network for the HDN of isoquinoline is also presented.     

Hydrodenitrogenation Catalysis

Catalytic hydrodenitrogenation (HDN) is a process in which organonitrogen compounds are removed from hydrocarbon feedstocks to produce processible, stable, and environmentally acceptable liquid fuels and lube base stocks. When coupled with hydrodesul-furization (HDS), this process is commonly referred to as “hydro-treating,” which is an integral part of oil refining. While it has long been recognized that HDN is more difficult than HDS, the former has historically been of little concern to the refiners because of the comparatively small quantities of nitrogen compounds present in conventional petroleum stocks. This situation, however, will certainly change because of the growing need to process heavy and low-quality stocks, and the anticipated need to upgrade syncrudes, both of which are rich in highly refractory nitrogen compounds. At present, conventional HDS catalyst technology is adapted for HDN, despite the fact that it is not ideally suited for nitrogen removal. In recent years there has been considerable interest in the development of more effective HDN catalysts, as witnessed by the rapidly expanding patent literature in this area.     

GC-AED法研究催化裂化柴油中硫氮化合物

采用气相色谱-原子发射光谱（GC-AED）联用技术对FCC柴油中的含硫化合物、含氮化合物进行定性定量研究。结果表明：FCC柴油中硫化物的类型主要是噻吩类衍生物、苯并噻吩、苯并噻吩类衍生物、二苯并噻吩、二苯并噻吩类衍生物，其中苯并噻吩类衍生物、二苯并噻吩类衍生物的硫质量分数占总硫质量分数的93．6％以上。氮化物主要为碱性氮化物（Nb）和非碱性氮化物（Np）两大类型，其中碱性氮化物主要是苯胺及其衍生物，喹啉含量很低，约占总氮质量分数的0．1％，非碱性氮化物主要包括吲哚及其衍生物和咔唑及其衍生物，而咔唑类氮化物一般约占总氮质量分数的64％。不同来源的FCC柴油，其所含硫化物、氮化物的含量和分布不同。应根据其硫化物、氮化物的分布类型及规律，开发合适的柴油脱硫脱氮催化剂及相关工艺。     

还原条件对磷化镍催化剂的HDN性能影响

采用原位还原技术制备出Ni2P/TiO2-Al2O3催化剂,在连续流动固定床高压微反装置中,以喹啉为模型化合物对催化剂的加氢脱氮性能进行评价。考察了原位还原条件及加氢工艺条件对催化剂的加氢脱氮性能的影响。确定了最佳还原条件:氢气流速100 mL/min,还原终温550℃,还原压力1 MPa,还原时间150 min;反应条件为:温度360℃、压力3 MPa、空速3 h-1、氢油比500∶1。最适宜反应条件下喹啉的脱氮率为98%。     

煤直接液化低分油加氢脱硫脱氮反应动力学研究

为了进一步了解煤直接液化油中硫氮化合物的形态和性质,采用石油研究中的先进分析手段GC-PFPD和GC-NCD,对煤直接液化低分油进行了分析,获得了详细的硫氮化合物组成含量。结果发现:煤直接液化低分油中含有大量的杂环化合物,S主要以苯并噻吩类和二苯并噻吩类化合物存在,N主要以五元环化合物形式存在。在高压釜中进行了催化剂添加量和不同温度条件下的加氢实验,对总硫总氮的加氢反应动力学进行了研究。通过计算得到了高压釜煤液化油加氢脱硫反应的一级反应动力学模型,且通过模型计算的S含量与反应实测的S含量相对误差仅为7.8%;对实验得到的震荡式高压釜中煤液化油加氢脱氮反应的一级反应动力学模型进行验证,发现相对误差也仅为0.97%。     

Investigation of hydrodearomatization of prehydrogenated gas oil fractions on Pt–Pd/H-USY catalysts

Hydrodearomatization (HDA), hydrodenitrogenation (HDN) and hydrodesulphurization (HDS) of real gas oils (various sulphur, nitrogen and total aromatic content) was investigated over Pd, Pt catalysts supported on USY zeolite, whose Pd/Pt mass ratio was varied between 6:1 and 1:3, and total metal contents were between 0.90 and 0.93. The effect of Pd/Pt ratio on HDA, HDN and HDS activities is presented. The advantageous process parameters for HDA, HDN and HDS of gas oils over a selected catalyst (e.g. Pd/Pt mass ratio 3:1) were determined. Additionally, the effect of key process parameters (temperature, pressure, LHSV) on the yield and quality of products was studied. Under optimal process parameters the HDA efficiency decreased with sulphur and nitrogen content of feed. The rate of HDA enhanced with Pt content of the catalyst while HDS and HDN efficiency increased with Pd content. The maximum aromatic saturation was 85% and it decreased with sulphur and nitrogen content of the feed.     

C—N键催化氢解反应研究进展

叙述了非杂环类含氮化合物和杂环类含氮化合物C—N氢解反应常用催化剂,讨论了苄基型含氮化合物的底物结构、催化剂及反应条件对C—N氢解反应的影响,初步探讨了C—N键催化氢解反应机理。认为C—N键的催化氢解反应不仅与含氮化合物的分子结构有关,还与催化剂的性能有关,若要从根本上提高C—N键氢解活性还需深入对反应机理的研究。     

Effect of temperature on activity and selectivity of carbon supported Mo sulfide in simultaneous hydrodenitrogenation of pyridine and hydrodesulfurization of thiophene

Activity and selectivity of carbon supported Mo catalyst was tested in parallel hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene in the temperature range 260–350 °C at 2 MPa of hydrogen pressure and compared with that of commercial NiMo-alumina catalyst Shell 324. The main advantages of carbon supported Mo sulfide over commercial NiMo catalyst can be summarized as follows: the markedly higher HDN and better HDS activities normalized to moles of active metals, the lower content of piperidine in the reaction products and the distinctly better selectivity towards HDN reaction.