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。     

复合氧化物在柴油加氢脱硫催化剂中的应用

加氢脱硫是石油炼制中的一个重要工艺过程,近年来,随着环境法规的日益严格和高硫原油加工量的增加,传统的加氢脱硫催化剂已经不能满足深度脱硫的要求,迫切需要开发新型深度加氢脱硫技术及催化剂,而复合氧化物载体能克服单一载体的缺陷,从而使制备的催化剂对芳烃的加氢和对二苯并噻吩及它的芳烃衍生物的转化具有较好的效果。综述了近年来复合氧化物载体在柴油加氢脱硫催化剂中的最新研究,重点介绍了含Al2O3、含TiO2和含ZrO2的复合氧化物载体的应用。     

TiO2及其复合载体在加氢脱硫中的应用研究进展

本文对TiO2载体的应用情况作了综述,并对TiO2与传统载体的使用性能进行对比,指出了TiO2载体的优势和存在的问题,并提出了解决问题的方法。     

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。     

复合SiO_2-Al_2O_3载体制备及其在柴油深度加氢脱硫中的应用

采用不同方法制备系列复合SiO_2-Al_2O_3载体,以等体积浸渍法负载硝酸镍和钼酸铵溶液制得加氢脱硫催化剂。通过BET、XRD和NH3-TPD对载体进行表征,并以直馏柴油为原料,考察不同载体对催化剂加氢脱硫活性的影响。结果表明,以硅质量分数27%的Si-Al-2载体负载浸渍液制得的催化剂具有较高的加氢脱硫活性,346℃可以将柴油中的硫含量脱除至小于10μg·g-1,加氢脱硫活性较对比剂有很大提高。     

柴油加氢脱硫催化剂的研究进展

以二苯并噻吩（DBT）为例介绍了其加氢脱硫（HDS）的反应网络，并对近年来国内外柴油加氢脱硫催化剂的研究进展加以综述，认为加氢脱硫技术仍是目前国内生产清洁柴油的重要手段。     

CL-03柴油深度加氢脱硫催化剂开发

以Y改性载体Z-1、Z-2、Z-3担载钼镍钨活性组分,制备了深度加氢脱硫催化剂CL-01、CL-02和CL-03,并进行了相关评价对比试验。结果表明:以Z-3制备的催化剂CL-03活性最佳;与工业剂R-1相比,催化剂CL-03具有更高的脱硫氮活性,其在反应温度360℃,体积空速3 h-1,氢油比250∶1,压力4 MPa条件下的相对脱硫活性为136.9%,相对脱氮活性为147.2%。在考察范围内,催化剂CL-03脱硫率最高达99.87%,产品硫含量7.6μg·g-1,满足柴油国V的硫含量标准。     

石油加氢脱硫催化剂载体的研究

介绍了目前加氢脱硫催化剂载体的种类和研究现状,包括氧化物载体、介孔分子筛载体、活性炭载体、酸碱载体等。分析了不同载体所具有的的优缺点,并展望了未来载体的研究方向。     

加氢脱硫催化剂载体的研究现状

介绍了目前加氢脱硫催化剂所应用载体的种类和研究现状,分析了不同载体所具有的各自的优缺点,对目前载体的各种研究进行了综述,同时也展望了未来载体的发展方向。     

Spherical mesocellular silica foams: a superior support for hydrodesulfurization of fluid catalytic cracking diesel

High surface area aluminum containing spherical mesocellular silica foams (SMCFs) with ultra-large pore volume and 3D pore size were successfully synthesized through a simple hydrothermal route, and the as-synthesized aluminum containing SMCFs (Al-SMCFs) was applied as the support of NiMo-base catalyst for the hydrodesulfurization (HDS) of fluid catalytic cracking (FCC) diesel. The as-synthesized supports and corresponding catalysts were characterized by powder small X-ray diffraction, nitrogen physisorption, scanning electron microscopy, transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy, and temperature-programmed reduction with H₂. The characterization results showed that, compared with other prepared catalysts (NiMo/Al-SBA-15 and NiMo/Al-KIT-6), the NiMo/Al-SMCFs catalyst possessed the most optimal physicochemical parameters, i.e., ultra-large 3D pore size (42.0 nm), high surface area (330.1 m²·g^?1), and ultra-large pore volume (1.96 cm³·g^?1), resulting in the formation of more homogeneous distribution of octahedral Mo active species and good mass transfer performance. Consequently, the NiMo/Al-SMCFs catalyst displayed the outstanding HDS performance (98.8%) of FCC diesel, confirming that the Al-SMCFs may be a type of promising candidate for oil hydrotreating.     

Nanosized HY zeolite-alumina composite support for hydrodesulfurization of FCC diesel

A series of hydrodesulfurization (HDS) NiMo catalysts supported on Al₂O₃-NY (denoted as ANY) composites with various amounts of nanosized H-type Y zeolite (denoted as NY) were prepared. The samples were characterized by XRD, BET, TPD, TPR, HRTEM, and FT-IR spectroscopy of pyridine adsorption. The characterization results showed that, compared with NiMo/Al₂O₃, the addition of NY reduced the Metal-support interaction and made the MoS₂ stacking degree higher, slabs shorter and dispersion of edge and corner Mo atoms bigger. The addition of NY also enhanced the overall acidity and the ratio of Brönsted acid to Lewis acid of these catalysts. The fluidized catalytic cracking (FCC) diesel HDS activity was increased with the addition of NY in these catalysts compared with NiMo/Al₂O₃ catalysts. The optimal NY content was found to be 20 wt% in ANY composite support. The highest HDS activity of NiMo/ANY20 was attributed to the synergy of hydrogenation activity, acid amount and textural properties.     

Synthesis and catalytic performance of novel hierachically porous material beta-MCM-48 for diesel hydrodesulfurization

Novel hierachically porous material Beta-MCM-48 was successfully synthesized from Beta zeolite seeds by two-step hydrothermal crystallization method using Cetyltrimethylammonium Bromide as the mesostructure directing agent. Beta-MCM-48 composite synthesized at the optimization conditions possessed Beta microporous structure and cubic Ia $ \overline{ 3} $ 3 ¯ d mesoporous structure simultaneously. Meanwhile, the acidity of Beta-MCM-48 was similar to Beta zeolite and higher than MCM-48 mesoporous material. A series of Al₂O₃-Beta-MCM-48 supported NiMo catalysts with different Beta-MCM-48 contents were prepared by the incipient-wetness impregnation method. The catalytic performances were evaluated using DaQing Fluid Catalytic Cracking diesel as feedstock in a high pressure microreactor. Hydrodesulfurization results indicated that NiMo/Al₂O₃-Beta-MCM-48 catalyst exhibited better activities than that of NiMo/Al₂O₃ traditional catalyst. NiMo/Al₂O₃-Beta-MCM-48 catalyst obtained the highest activity as the Beta-MCM-48 content in the support was 20 wt %, and the corresponding sulfur content of the hydrotreated product reached to 23.02 μg g^?1.     

催化汽油选择性加氢脱硫技术OCT-MD的工业应用研究

分析了OCT-MD技术工业应用中出现的辛烷值损失大的原因,研究了预分馏过程烯烃、硫化合物在轻重馏分的分布规律,提出了降低辛烷值损失的措施,确定了适宜的加氢反应温度为285~290℃,并根据工业装置运行数据对加氢催化剂的选择性进行了评价。     

柴油加氢脱硫RS-1100催化剂的工业生产与应用

中国石油化工股份有限公司石油化工科学研究院为进一步提高柴油加氢脱硫催化剂性能,降低催化剂成本,增强市场竞争力,成功开发了新型NiMo类柴油超深度加氢脱硫RS-1100催化剂,并进行了工业生产,获得成功应用。中国石油化工股份有限公司济南分公司工业应用结果表明,RS-1100催化剂在较低反应温度下具有较高的脱硫、脱氮活性,能够满足生产国Ⅲ和国Ⅳ标准柴油要求。中国石油化工股份有限公司沧州分公司工业应用结果表明,RS-1100催化剂具有良好的加氢脱硫和加氢脱氮活性,能够满足生产国Ⅲ标准柴油要求,并有进一步提高油品质量的空间。     

柴油车NOx选择性催化还原技术研究进展

综述了NH<,3>-SCR技术的反应机理、国内外不同催化体系针对NOx脱除的研究现状及NH<,3>-SCR技术涉及的其他关键技术,并对选择性催化还原技术的发展方向进行了展望.     

加氢法与生物法联合脱除催化柴油有机硫探索实验

由于存在空间位阻,二苯并噻吩(DBT)及其烷基化衍生物(Cx-DBT)中的硫原子很难与加氢催化剂接触.因此,作为柴油脱硫的主要工艺,加氢催化对于柴油中的主要有机硫化物DBT和Cx-DBT的脱除率比较低,难以实现深度脱硫.针对硫质量分数为3 358 μg/g的催化柴油,采用加氢脱硫与生物脱硫相结合的办法进行处理后,催化柴油的硫质量分数降低到20μg/g以下,使用气相色谱-原子发射仪对柴油脱硫前后的硫分布进行检测,发现2种工艺的结合能有效地脱除催化柴油组分中绝大多数的DBT和Cx-DBT,显示出良好的应用前景.     

Preparation and catalytic performance of modified kaolin clay with big pore for the hydrodesulfurization of diesel

A kind of metakaolin materials with big pores was prepared from natural kaolin clays. The prepared metakaolin was introduced into alumina as composite support for hydrotreating application. A series of nickel–tungsten catalysts (NiO 2.9 wt%, WO₃ 27.2 wt%) supported on alumina-metakaolin, alumina-titania and bare alumina also were prepared. Electron microprobe analysis including SEM and TEM, BET and temperature programmed desorption of NH₃ were used for the samples characterization. Their hydrodesulfurization (HDS) activity for diesel were evaluated and compared. The results showed that NiW/alumina-metakaolin had excellent HDS activity and alumina-metakaolin support could be a good candidate support for hydrotreating catalysts.     

柴油加氢脱硫催化剂的选择

在连续流动固定床加氢装置上,考察Co-Mo型催化剂和Ni-W型催化剂在不同操作条件以及不同脱硫深度下的加氢脱硫反应性能。结果表明,两种催化剂对操作压力改变的敏感度不同;在不同的脱硫深度下,对不同的原料油也表现出不同的脱硫活性。