过渡金属磷化物催化剂综述

过渡金属磷化物催化剂具有特殊的晶体结构,在催化加氢脱硫、加氢脱氮及电化学制氢反应中具有优异的催化活性。主要简述过渡金属磷化物催化剂的结构、制备方法和应用。多金属、复合多功能型过渡金属磷化物催化剂将在催化制氢反应中受到更多的关注。     

Ni2P催化剂的制备及其在加氢脱硫的研究进展

现在油品重质化越来越严重,为了满足环境保护局和人们的要求,对油品加氢脱硫已是一项急迫的任务。过渡金属磷化物具有优异的加氢脱硫活性和稳定性,尤其是Ni2P催化剂,将成为催化材料领域研究的热点。本文综述了Ni2P催化剂制备方法和加氢脱硫活性。Ni2P催化剂有望成为继硫化物、碳化物催化剂之后的又一代深度加氢脱硫催化剂。     

过渡金属磷化物的改性方法及其在电化学析氢中的应用

过渡金属磷化物催化活性高、稳定性好，是电催化析氢的良好催化剂。然而，实现过渡金属磷化物在电解水制氢领域的大规模应用，还需要进一步提升其催化性能。本文以过渡金属磷化物的组成变化为出发点，从金属/磷（M/P）化学计量比的角度对过渡金属磷化物的性能进行了总结，介绍了其常见的制备方法，详细综述了元素掺杂、构造缺陷、构建界面工程、耦合炭材料、调控微观结构、改善材料浸润性等改性方法对过渡金属磷化物电催化制氢性能的影响。最后在新型磷源的开发、测试标准化、晶面调控等方面对过渡金属磷化物的发展趋势进行了展望。     

过渡金属磷化物制备与加氢脱硫性能研究进展

近年来油品重质化越来越严重,环保法规要求也日趋严格,为满足环境保护和人们的需求,对油品的加氢脱硫成为一项紧迫任务。综述了近年来过渡金属磷化物在复合载体和制备方法等方面的最新研究进展情况,其中具体介绍了程序升温还原法及低温热分解法,同时概述了过渡金属磷化物的加氢脱硫性能。     

过渡金属磷化物的结构、性质及制备方法

由于过渡金属磷化物的特殊结构,使其具有类似于贵金属的性质,被人们称为"准铂催化剂",且具有高的活性,高的稳定性和抗硫中毒等性能,在催化加氢、脱硫、脱氮、光催化等方面表现出了比商业用催化剂更好的性能,近年来成为新的研究热点。本文综述了过渡金属磷化物的结构、性质及制备方法,重点介绍了过渡金属磷化物的不同制备方法。     

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。     

高硫原油中硫化物的脱除工艺及脱硫剂

负载型过渡金属磷化物馏分油深度加氢脱硫催化剂制备方法属于新材料、石油炼制和石油化工技术领域。是采用一种新型的载体材料担载金属活性组分，并用一种新的活化方法合成表面金属磷化物，制备石油炼制工业中所用汽油、煤油、柴油、蜡油等馏分油深度加氢脱硫催化剂的方法，新型载体材料是指由中孔分子筛与多孔氧化物构成的复合载体，该方法制备出了高活性的加氢脱硫催化剂。有益效果是，可将石油馏分油中最难脱除的二苯并噻吩及其衍生物几乎全部转化。主要用于制造炼油加氢精制催化剂和石油化工生产中原料预精制加氢脱硫催化剂。     

克劳斯尾气加氢脱硫催化剂及其作用机理研究进展

介绍了国内外克劳斯尾气加氢脱硫催化剂的技术发展及其基础理论研究进展,包括CoMo催化剂的结构研究及催化加氢脱硫机理,新型非CoMo过渡金属硫化物催化剂和过渡金属碳化物、氮化物以及磷化物催化剂、螯合剂对CoMo催化剂的改性及其作用机理,新型CoMo催化剂载体和γ-Al₂O₃载体的复合改性。     

过渡金属氮化物制备方法及吸氢机理研究进展

介绍了过渡金属氮化物的制备方法,讨论了影响程序升温氮化法的因素;分析了过渡金属氮化物催化剂的吸氢活性、吸附机理.与传统的过渡金属硫化物催化剂相比具有更加优异的氢吸附、活化和转移能力.在加氢脱硫、加氢脱氮和其他涉氢反应中有着广泛的应用.     

煤焦油加氢脱硫脱氮催化剂研究进展

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和氮污染环境,各国对油品中的硫和氮含量进行了严格限制,脱硫和脱氮成为煤焦油化工行业的重要课题。介绍煤焦油加氢工艺,综述金属碳化物、氮化物、磷化物和硫化物作为催化剂的研究现状。贵金属催化剂具有较强的加氢能力,并且通过使用强酸性载体分子筛和双金属催化剂的方法提高贵金属催化剂的抗硫毒性。碳化物催化剂具有较高的熔点和硬度、较好的机械稳定性和热稳定性,室温下几乎可以耐各种腐蚀性物质。根据金属源和碳源的不同,介绍使用程序升温还原法、气相法、热分解法和液相反应法制备碳化物催化剂的制备工艺。过渡金属磷化物催化剂具有优异的加氢脱硫和加氢脱氮选择性,添加钒的磷化物催化剂能改变加氢脱氮路径的选择性,明显增加咔唑加氢脱氮反应活性,钙的添加明显提高磷化物催化剂的加氢脱硫活性。工业上通常以ⅥB族和ⅧB族金属为活性物质制备过渡金属硫化物催化剂,使用的贵金属主要包括Pt、Pd和Ru,非贵金属主要包括W、Mo、Co和Ni等,其中,贵金属通常使用Al₂O₃或SiO₂为载体。ZrO₂载体可与活性组分产生较强的相互作用,热力学稳定性较高,但比表面积小,价格昂贵。Al₂O₃载体机械强度大,比表面积高,ZrO₂-Al₂O₃复合载体将两者的优良性能结合,可以获得性能更加优异的载体。     

Hydrodesulfurization of hindered dibenzothiophenes: an overview

Hydrodesulfurization is a well-documented process which has been commonly used in the refining of crude oil for over 60 years. It is a process for which interest is frequently renewed due to the requirement to use new feedstocks and the application of more severe environmental legislation, for example, the need to reduce sulfur levels in fuels. Of particular importance in achieving low sulfur levels in fuels is the problem posed by a particular class of compounds, namely hindered dibenzothiophenes, e.g. dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Dibenzothiophenes demonstrate resilience to hydrodesulfurization using current catalyst formulations. This overview addresses the key area of hydrodesulfurization chemistry concerning the desulfurization of highly hindered sulfur containing molecules.     

放射性35S同位素示踪技术在加氢脱硫反应研究中的应用

过渡金属硫化物催化剂广泛应用于石油炼制催化加氢过程。催化剂活性相的结构与加氢脱硫性能的关系一直是催化研究的热点。放射性³⁵S同位素示踪技术由于能够在线分析硫化态催化剂上硫的性能而备受关注。综述了放射性³⁵S示踪技术在辅助研究加氢脱硫催化剂预硫化过程、加氢脱硫反应机理及催化剂上硫的性能中的应用。     

载体对FCC汽油加氢脱硫催化剂性能的影响

主要介绍了载体的种类及性能对FCC汽油加氢脱硫效果的影响。指出在制备FCC汽油加氢脱硫催化剂时,应选择具有适当酸碱度的物质作为载体,保证催化剂具有较高的加氢脱硫／加氢选择性,从而使脱硫后的FCC汽油满足低硫含量高辛烷值的要求。     

Activities of unsupported second transition series metal sulfides for hydrodesulfurization of sterically hindered 4,6‐dimethyldibenzothiophene and of unsubstituted dibenzothiophene

The applicability of transition metal sulfides (TMS) from the second transition series in deep hydrodesulfurization (HDS) was examined and compared to that of a traditional, supported CoMo/Al₂O₃ catalyst. Sulfides of Nb, Mo, Ru, Rh and Pd were studied for HDS of dibenzothiophene (DBT) and 4,6‐dimethyldibenzothiophene (4,6‐Me₂DBT). Measurements were carried out with unsupported TMS samples at different temperatures and H₂S partial pressures. The trend in DBT HDS activities agreed quite well with those found by previous authors. It was furthermore found that the activities of the metal sulfides towards the sterically hindered molecule 4,6‐Me₂DBT closely followed those for DBT. This is somewhat surprising since the direct sulfur abstraction route was of major importance for DBT while the prehydrogenation route, in which ring‐hydrogenation in the DBT skeleton precedes desulfurization, was prevalent for 4,6‐Me₂DBT. This suggests that common steps are involved in the two routes. For the unsupported metal sulfides, ring‐hydrogenated but not desulfurized DBT and 4,6‐Me₂DBT products were found in much larger amounts than for supported and promoted MoS₂‐based catalysts. This can be rationalized as being due to a relatively higher hydrogenation/desulfurization selectivity ratio for the different transition metal sulfides. Inhibition by H₂S was found to be most pronounced near the center of the transition series. This revised version was published online in July 2006 with corrections to the Cover Date.     

焦炉气加氢催化剂及净化工艺的开发

介绍了适合于焦炉气加氢催化剂及净化工艺的研究实验结果,实验表明,JT-1及JT-8型加氢催化剂均可适用于含高浓度CO和CO2气氛下原料气的加氢净化,且净化度高,副反应小,并满足以焦炉气为原料的甲醇厂的原料净化要求,可将原料气中硫化物脱除至总硫体积分数<0.1×10-6。     

MCM-41-supported Co-Mo catalysts for deep hydrodesulfurization of light cycle oil

Light cycle oil (LCO), a by-product of the fluid catalytic cracking (FCC) process in a petroleum refinery, can be used as a blendstock for the production of diesel and jet fuels. Regulatory and operational issues result in need for new and more active catalysts for the deep hydrodesulfurization (HDS) of diesel feedstocks, such as LCO. This paper reports the activity of a mesoporous molecular sieve MCM-41-supported Co-Mo catalyst in comparison to a commercial γ-alumina (Al₂O₃)-supported Co-Mo catalyst for the desulfurization of a LCO with a sulfur content of 2.19 wt.%. The HDS of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene—polyaromatic sulfur compounds present in LCO—and their relative reactivities in terms of conversion were examined as a function of time on stream in a fixed-bed flow reactor. The MCM-41-supported catalyst demonstrates consistently higher activity for the HDS of the refractory dibenzothiophenic sulfur compounds, particularly 4,6-dimethyldibenzothiophene. The presence of a large concentration of aromatics in LCO appears to inhibit the HDS of the substituted dibenzothiophenes.     

Development of ultra-deep HDS catalyst for production of clean diesel fuels

Cosmo Oil has successfully developed a new CoMo HDS catalyst, C-606A, for production of ultra-low sulfur diesel fuels. This catalyst was prepared by an impregnation method using a solution containing Co, Mo, P, and citric acid on a HY-Al₂O₃. The resulting catalyst air-dried only without calcination. The HDS activity was measured with straight-run light gas oil feedstocks under industrial hydrotreating conditions. C-606A had a three times higher HDS activity compared with the conventional CoMoP/Al₂O₃ catalyst. Commercial operation with C-606A has successfully demonstrated high performance. This catalyst has superior activity, which enables <10-ppm sulfur content in products in a commercial hydrotreater designed to produce 500-ppm sulfur diesel fuels.     

Science and technology of novel processes for deep desulfurization of oil refinery streams: a review

Oil refinery related catalysis, particularly hydrodesulfurization (HDS) processes, is viewed as a mature technology and it is often stated that break-throughs are not to be expected. Although this could be a justified compliment to those who developed this area, at the same time it could also stifle potential new ideas.The applicability and perspectives of various desulfurization technologies are evaluated taking into account the requirements of the produced fuels. The progress achieved during recent years in catalysis-based HDS technologies (synthesis of improved catalysts, advanced reactor design, combination of distillation and HDS) and in ‘non-HDS’ processes of sulfur removal (alkylation, extraction, precipitation, oxidation, and adsorption) is illustrated through a number of examples.The discussed technologies of sulfur removal from the refinery streams lead to a wealth of research topics. Only an integrated approach (catalyst selection, reactor design, process configuration) will lead to novel, efficient desulfurization processes producing fuels with zero sulfur emissions.     

油品深度加氢脱硫催化研究进展

汽油深度脱硫的关键是在脱硫同时避免辛烷值的下降和汽油收率的损失;柴油深度脱硫的关键是对反应活性最低的4,6-二甲基苯并噻吩类化合物中硫原子的脱除,并克服原料中多环芳烃和含氮物以及产物中H2S对脱硫效果的抑制作用.本文概述了汽油和柴油深度脱硫催化剂在工业应用方面的研究进展,综述了加氢脱硫催化剂基础研究方面的最新动态;强调了在分子和原子水平上认识加氢脱硫催化剂微观结构和反应机理对研发超高活性及选择性深度脱硫催化剂的指导作用.