国外柴油加氢脱硫催化剂的研究进展

硫含量是柴油燃料质量升级最主要的制约因素.与其他方式相比,最为经济简便的脱硫手段是采用更高活性的加氢脱硫催化剂.重点介绍了国外在开发柴油深度加氢脱硫催化剂方面所取得的进展.     

FH-UDS柴油深度加氢脱硫催化剂的工业应用

主要介绍FH-UDS柴油深度加氢脱硫催化剂在260万t/a柴油加氢精制装置的首次工业应用情况,并对该催化剂的性能及使用效果进行分析,着重分析了催化剂对柴油的深度脱硫能力.工业应用结果表明:FH-UDS柴油深度加氢脱硫催化剂具有良好的加氢脱硫、脱氮活性和稳定性,能够满足柴油加氢精制装置生产低硫柴油和高负荷运行的要求;对操作条件进行适当调整,可以生产出硫质量分数小于10μg/g超低硫柴油.     

影响柴油深度加氢脱硫的主要因素

研究了在柴油深度加氢脱硫反应过程中,原料油的性质、工艺条件、催化剂的活性及催化剂的合理匹配等因素对加氢脱硫率的影响.     

车用燃料油精制脱硫的研究与发展

降低车用燃料油中硫含量对于提高机动车尾气排放质量从而保护环境具有十分重要的意义。着重对催化加氢及非催化加氢脱硫两类加氢工艺的特点进行了比较,介绍了国内外车用燃料油精制脱硫的研究与发展。针对开发新配方汽油及低硫、低芳烃柴油的要求,提出了今后燃料油脱硫的研究方向为:具有较高选择性的汽油加氢脱硫催化剂和新工艺;具备高效加氢脱硫和芳烃饱和活性的新一代柴油改质催化剂和新工艺;同时应重视非催化加氢脱硫技术的应用研究。     

柴油深度加氢脱硫技术进展

随着世界各国对环保法规的日益关注,运输燃料深度脱硫技术在世界范围内受到广泛的研究。近年来,柴油深度脱硫化技术已受到西方国家的普遍重视。在工业上,加氢工艺是应对产品低硫化最有效的途径。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。本文综述了近年来柴油深度加氢脱硫技术的基本原理、超低硫柴油的催化及工艺的研究进展。     

汽油和柴油中含硫化合物加氢脱硫反应机理研究进展

环境保护意识的大幅度提升促使车用燃料质量标准日益严格,为实现汽油和柴油中硫含量不断降低的目标,迫切需要研发超深度脱硫技术.目前加氢脱硫技术是大规模工业化应用的关键技术,其核心是高效催化剂的研制.介绍了FCC汽油及柴油中所含各类硫化物的加氢脱硫反应路径,主要讨论了其中难以脱除的噻吩类、苯并噻吩类、二苯并噻吩类和4,6-二...     

柴油加氢脱硫催化剂的研究进展

随着环保问题越来越受到世界各国的重视,各国相继推出了高质量的清洁燃料标准。低硫化是柴油清洁利用的发展趋势,研制开发高效稳定的加氢脱硫催化剂是加氢脱硫技术研究的主要方向之一。本文主要阐述了国内外在柴油加氢脱硫方面的研究成果,主要分析了柴油加氢脱硫反应机理、柴油加氢脱硫催化剂的主催化剂、助剂和载体的研究进展。分析表明,柴油加氢脱硫的主要路径是直接脱硫和加氢路径,而柴油中受空间位阻影响大的4.6-二甲基二苯并噻吩的脱除路径主要是加氢路径和烷基转移路径。文章从柴油加氢脱硫催化剂的组成和结构分析了催化剂的加氢脱硫机理,得到加氢脱硫活性与催化剂的表面微观结构紧密相关。分析了近年来催化剂载体的研究进展,发现柴油加氢脱硫催化剂的载体主要是氧化铝及改性的氧化铝。     

水热处理对体相加氢催化剂活性的影响

体相催化剂经水热处理后,催化剂孔结构发生了改变,孔容、孔径和比表面积增加。采用小型加氢装置加工处理不同超深度脱硫难度的柴油原料,对水热处理后的催化剂进行超深度加氢脱硫活性评价。评价结果表明,体相催化剂经水热处理后,提高体相催化剂的超深度加氢脱硫活性和芳烃饱和性能,加工处理超深度脱硫难度大的劣质柴油时,加氢活性提高更加明显。以直馏柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,对比没经水热处理的催化剂,水热处理后催化剂的反应温度降低了5℃。而以催化柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,水热处理后催化剂的反应温度比水热处理前的反应温度降低了13℃。水热处理后的体相催化剂具有良好的活性稳定性。     

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。     

FCC汽油加氢脱硫催化剂研究进展

介绍了国内外FCC汽油中硫存在形式、加氢脱硫反应原理以及研究进展。通过对加氢脱硫活性相结构和其与催化剂活性关系的分析,对不同加氢脱硫制备方法进行分析,对加氢脱硫催化剂的载体、活性组分、助剂方面加以分析,可知发展高活性、高选择性的催化剂仍是现今研究的热点。     

An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel

This review discusses the problems of sulfur reduction in highway and non-road fuels and presents an overview of new approaches and emerging technologies for ultra-deep desulfurization of refinery streams for ultra-clean (ultra-low-sulfur) gasoline, diesel fuels and jet fuels. The issues of gasoline and diesel deep desulfurization are becoming more serious because the crude oils refined in the US are getting higher in sulfur contents and heavier in density, while the regulated sulfur limits are becoming lower and lower. Current gasoline desulfurization problem is dominated by the issues of sulfur removal from FCC naphtha, which contributes about 35% of gasoline pool but over 90% of sulfur in gasoline. Deep reduction of gasoline sulfur (from 330 to 30 ppm) must be made without decreasing octane number or losing gasoline yield. The problem is complicated by the high olefins contents of FCC naphtha which contributes to octane number enhancement but can be saturated under HDS conditions. Deep reduction of diesel sulfur (from 500 to <15 ppm sulfur) is dictated largely by 4,6-dimethyldibenzothiophene, which represents the least reactive sulfur compounds that have substitutions on both 4- and 6-positions. The deep HDS problem of diesel streams is exacerbated by the inhibiting effects of co-existing polyaromatics and nitrogen compounds in the feed as well as H₂S in the product. The approaches to deep desulfurization include catalysts and process developments for hydrodesulfurization (HDS), and adsorbents or reagents and methods for non-HDS-type processing schemes. The needs for dearomatization of diesel and jet fuels are also discussed along with some approaches. Overall, new and more effective approaches and continuing catalysis and processing research are needed for producing affordable ultra-clean (ultra-low-sulfur and low-aromatics) transportation fuels and non-road fuels, because meeting the new government sulfur regulations in 2006–2010 (15 ppm sulfur in highway diesel fuels by 2006 and non-road diesel fuels by 2010; 30 ppm sulfur in gasoline by 2006) is only a milestone. Desulfurization research should also take into consideration of the fuel-cell fuel processing needs, which will have a more stringent requirement on desulfurization (e.g., <1 ppm sulfur) than IC engines. The society at large is stepping on the road to zero sulfur fuel, so researchers should begin with the end in mind and try to develop long-term solutions.     

On the hydrodesulfurization of FCC gasoline: a review

The possible origins of sulfur impurities in FCC gasoline are reviewed and discussed. Their mechanism of formation during the FCC process as well as their mechanism of transformation on hydrotreating catalysts are also examined.The article focuses on the desulfurization of FCC gasoline by means of catalytic processes considering the fact that deep desulfurization must be achieved (in accordance with new regulations) while preserving octane rating of the fraction. The various parameters (presence of a promoter, nature and modification of the support, additives and poisons) which may influence the selectivity in hydrodesulfurization (HDS) versus olefin hydrogenation are also discussed. Existing and potential processes for the HDS of FCC gasoline with octane preservation are described.     

V-Mo based catalysts for oxidative desulfurization of diesel fuel

Catalytic oxidative desulfurization (ODS) of a Mexican diesel fuel on a spent HDS catalyst, deactivated by metal deposits, was carried out during several reactive-batch cycles in order to study the catalytic performance to obtain low sulfur diesel. To explain catalytic activity results, Mo and/or V oxides supported on alumina pellets were prepared and evaluated in the ODS of a model diesel using tert-butyl hydroperoxide (TBHP) or H₂O₂ as oxidant. The catalytic results show that V-Mo based catalysts are more active during several ODS cycles using TBHP. The performance of the catalysts was discussed in terms of reduced species of vanadium oxide, prevailing on the catalysts, which increase the sulfone yield of refractory HDS compounds (DBT, 4-MDBT and 4,6-DMDBT).     

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.     

FCC汽油加氢脱硫反应过程及其催化剂研究进展

综述了国内外有关FCC汽油中硫的存在形态、HDS反应原理及其催化剂的研究进展.一般认为,FCC汽油中的硫化物形态主要为噻吩类化合物,且主要集中在重馏分中,汽油的HDS反应原理的研究也都集中在噻吩的加氢脱硫反应上.传统的HDS催化剂由于烯烃饱和率过高不适于FCC汽油的HDS,可通过改变催化剂的酸性来调整其HDS/HYD选...     

Oxidative Desulfurization of Hydrocarbon Fuels

New requirements for very low sulfur content (10 ppm) in liquid motor fuels demand novel approaches for ultra-deep desulfurization. For production of near-zero-sulfur diesel and low-sulfur fuel oil, removal of refractory sulfur compounds, like 4,6-dimethyldibenzothiophene and other alkyl-substituted thiophene derivatives, is necessary. Elimination of these compounds by hydrodesulfurization (HDS) requires high hydrogen consumption, high pressure equipment, and new catalysts. Various oxidative desulfurization processes, including recent advances in this field for diesel fuels, and the drawbacks of this technology in comparison with HDS are examined and discussed. It is shown that the oxidation of sulfur compounds to sulfones with hydrogen peroxide allows for production of diesel fuels with a sulfur content of 10 ppmw or lower at atmospheric pressure and room temperature. The gas phase oxidative desulfurization of sulfur compounds with air or oxygen is feasible at atmospheric pressure and higher temperatures: 90–300 °С and offers better economic solutions and incentives.     

燃料油加氢深度脱硫催化剂及工艺技术进展

分析了燃料油中硫化物的形态及加氢脱硫反应机理;介绍了国内外加氢深度脱硫催化剂的研究现状;评述了现有加氢深度脱硫反应工艺及反应器技术。     

Sulfided Mo and CoMo supported on zeolite as hydrodesulfurization catalysts: transformation of dibenzothiophene and 4,6-dimethyldibenzothiophene

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) and of 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out on sulfided Mo and CoMo on HY catalysts, and also on sulfided Mo and CoMo on alumina catalysts (fixed bed reactor, 330°C, 3 MPa hydrogen pressure). On all the catalysts, the two reactants transformed through the same parallel pathways: direct desulfurization (DDS) leading to biphenyl-type compounds, and desulfurization after hydrogenation (HYD) leading first to tetrahydrogenated intermediates, then to cyclohexylbenzene-type products. However, additional reactions were observed with the zeolite-supported catalysts, namely methylation of the reactants, cracking of the desulfurized products, and, in the case of 4,6-DMDBT, displacement of the methyl groups and transalkylation. The global activity of Mo/zeolite in DBT or 4,6-DMDBT transformation as well as its activity for the production of desulfurized products (HDS) were much higher than those of Mo/alumina. On the other hand, cobalt exerted a promoting effect on the activity in the transformation of DBT or 4,6-DMDBT of all the molybdenum catalysts. However, this effect was much less significant with the zeolite support than with the alumina support, which indicated that the promoter was not well associated to molybdenum on the zeolite support. Therefore, the activity of CoMo/zeolite in the HDS of DBT was much lower than that of CoMo/alumina. On the contrary, in the case of 4,6-DMDBT CoMo/zeolite was more active in HDS than CoMo/alumina. This increase in HDS activity was attributed to the transformation of 4,6-DMDBT into more reactive isomers through an acid-catalyzed methyl migration. The consequence was that on the zeolite-supported catalyst 4,6-DMDBT was more reactive than DBT.     

Deep hydrodesulfurization of diesel fuel: Design of reaction process and catalysts

Deep hydrodesulfurization (HDS) of diesel fuel oil was designed based on the recognition that alkyl dibenzothiophenes such as 4-methyl-and 4,6-dimethyldibenzothiophenes were the main target for deep HDS. Multi-stage and fractional HDS were very effective to achieve satisfactory HDS in terms of both sulfur level and fluorescent color of desulfurized oil. Catalysts with the selective hydrogenation of refractory sulfur species in major aromatic partners and isomerization-disproportionation of their alkyl groups prior to HDS were also designed to promote the desulfurization of such sulfur species.