液相吸附法燃油深度脱硫机理的研究进展

针对吸附脱硫的分子扩散和表面吸附两个过程。从分子尺寸选择、酸性位点吸附以及配位作用等方面综述了现有的吸附脱硫机理,介绍了各个机理指导下的液相吸附脱硫技术。指明了吸附脱硫机理的研究对开发高效燃油深度脱硫吸附剂和吸附脱硫新技术的指导意义。     

吸附法燃油超深度脱硫的研究进展

传统的加氢脱硫工艺能耗高且难以超深度脱硫,而吸附脱硫成本相对较低,可超深度脱硫。综述了吸附法燃油超深度脱硫的研究进展。吸附脱硫技术分为物理吸附脱硫和反应吸附脱硫。物理吸附脱硫技术存在的关键问题是,燃油中相对大量的芳烃和烯烃等组分会与有机硫化物形成强烈的竞争吸附,导致吸附剂脱硫选择性及脱硫量较低;反应吸附脱硫技术由于在吸附剂表面将有机硫转化成了其他形式的更易吸附的硫化物,然后再吸附脱除,因而吸附脱硫选择性较高。目前,还原型反应吸附脱硫技术S-Zorb工艺已投产,而近年来发展迅速的氧化型反应吸附脱硫技术由于可在常温常压下进行,且不消耗氢气,极具应用前景。     

燃料油液相吸附脱硫机理及研究进展

综述了燃料油液相吸附脱硫机理,分析了分子尺寸选择机理、酸性位吸附机理等液相物理吸附脱硫机理的特点,指出物理吸附脱硫技术对硫化物的选择性较差且较难实现深度脱硫.重点阐述了π络合机理和S-M配位机理及研究现状,并对络合配位吸附脱硫技术存在的问题及发展前景进行了评价和展望.吸附脱硫技术具有操作条件温和、脱硫效果好、烯烃不被饱...     

机动车燃油的脱硫技术及机理

介绍了世界燃油质量标准,简要报道了机动车用汽、柴油中硫化物的种类和含量,详细报道了燃油的加氢、生物、氧化和吸附脱硫机理及技术。噻吩类化合物占汽油总含硫量的83%,柴油中的硫主要以苯并噻吩及二苯并噻吩形式存在。吸附脱硫将会成为具有良好发展前景的燃油脱硫技术。插图6幅,数据表4张,参考文献37篇。     

车用燃料油吸附法深度脱硫技术进展

综述了车用燃料油吸附法深度脱硫的技术及吸附机理,主要包括物理吸附脱硫、化学吸附脱硫、络合吸附脱硫和选择性吸附脱硫等。物理吸附是极性吸附,吸附剂对硫化物的选择性差,难以对燃料油进行深度脱硫;化学吸附能对燃料油进行深度脱硫,但吸附温度和吸附剂再生温度较高;络合吸附和选择性吸附脱硫技术操作条件温和、投资和操作费用低,能深度脱硫,可生产硫含量小于50μg/g的低硫车用燃料油,但目前吸附剂对含硫芳烃的选择性和容硫量还较低,不能满足工业应用的要求。     

柴油吸附脱硫技术研究进展

吸附脱硫是一项具有广阔发展空间及应用前景的脱硫技术，具有操作简单、投资少、无污染、适合于深度脱硫等优点。详细介绍了S-Zorb diesel、MeND、IRVAD、PSU-SARS、Exxon diesel及其他吸附脱硫技术的研究进展情况。     

多孔材料吸附脱硫研究进展

选择性吸附技术因其具有工艺条件温和,操作简便,设备要求低,易再生等优点,在各种气体和液体脱硫中具有很好的前景和巨大的发展潜力,是常低温精脱硫领域的重要研究方向。综述了活性碳、分子筛、MOFs等多孔材料的结构,吸附脱硫机理及其在精脱硫中存在的问题,指出新型多孔材料MOFs应用于选择吸附精脱硫极具潜力。     

吸附法液化气脱硫研究进展

Merox抽提氧化脱硫法是目前液化气脱硫领域的主导技术,尽管如此,该方法由于存在脱硫深度低,碱液污染等一系列问题正处于改进阶段。吸附法脱硫作为一种清洁脱硫技术具有脱硫深度高、无碱排放等一系列优点而成为研究者们关注的热点。本文从目前吸附脱硫技术中常用的吸附剂入手,介绍了金属氧化物、活性炭、分子筛以及近些年流行的MOFs材料等吸附剂,归纳总结了脱硫原理、影响脱硫效果的因素、脱硫技术的研究与应用进展以及吸附剂的再生过程等。并对吸附法液化气脱硫技术进行了利弊分析,最后对吸附法液化气脱硫的技术前景做了展望。     

Mechanisms of selective absorption desulfurization technology for diesel and R & D development

阐述了近年来吸附脱硫技术在油品脱硫领域中的研究趋向及应用成果.首先分析讨论了催化吸附剂在油品中的物理和化学吸附脱硫机理;其次概述了以活性炭、分子筛等多孔性物质为载体的催化吸附剂在酸碱氧化、负载活性组分等改性方面和油品脱硫方面的最新应用和研究进展,对各类催化吸附剂的制备方法、吸附方法和脱硫效果进行了比较和总结;最终提出了催化吸附剂及吸附脱硫技术在柴油脱硫应用研究中存在的问题及今后的研究和发展方向.     

吸附脱除噻吩类硫化物机理的研究进展

针对反应型和非反应型吸附脱硫吸附剂,从实验研究和理论计算两方面,综述了噻吩类硫化物在金属、金属氧化物、分子筛等典型吸附剂表面的吸附原理、作用方式以及现阶段吸附脱硫机理的研究进展,指出虽然目前对吸附脱硫机理的研究仍未达成共识,但是计算研究已成为实验研究的有力辅助工具,为进一步探明吸附脱硫机理提供了有效途径。吸附脱硫机理是吸附剂优化的理论依托,对于指导高效、优化的吸附剂开发具有重要意义。     

燃料油选择性吸附脱硫研究进展

依据燃料油中硫化物与吸附剂表面活性点相互作用的类型,综述了π络合吸附、S—M配位吸附、酸性位吸附和多活性位吸附等选择性吸附脱硫方式的研究进展。认为通过结合多种选择性吸附原理,制备具有多种活性位的吸附剂,达到深度脱硫过程中高选择性和高吸附容量的目的,是燃料油深度脱硫吸附剂研究和开发的主要方向。     

汽油和柴油脱硫技术进展

对目前清洁燃料油的生产技术进行了概述。随着环境保护意识的增强，世界各国将实施更加严格限制燃料油中硫含量的新规定，为此进一步开展清洁燃料油生产技术具有重要的意义。结合现有的燃料油脱硫技术，深入开展催化吸附脱硫、生物脱硫技术及组合脱硫技术应当成为燃料油脱硫技术的研究重点。     

吸附功能膜的三维通道构建及其脱硫行为

以耐高温基聚合物聚酰亚胺(PI)为基质材料,以Y分子筛为功能颗粒,通过相转化法制备了吸附功能膜,用于燃料油的深度脱硫,采用FT-IR、XPS和电镜分析手段系统研究了该吸附功能膜的形态结构、通道与吸附脱硫性能的关系。结果表明,所制备的吸附功能膜具有发达的孔结构,功能颗粒镶嵌于基膜表面层的三维网络通道中。膜的孔结构随凝固浴介质的不同而有显著区别,以水、乙醇、异丙醇、正丁醇的顺序,从指状孔结构逐渐向海绵状孔结构过渡;挥发时间的增加有利于海绵状孔的形成,海绵状、指状孔通道共存有利于吸附功能的实现。AgY-PI膜的吸附性能高于NaY-PI膜,这与分子筛与硫化物的结合力大小有关;AgY-PI膜可将燃料油硫质量浓度降至0.1mg/L以下,为燃料油脱硫提供了一种新途径。     

Oxidative Desulfurization of Fuel Oil: Modeling Based on Artificial Neural Network

Oxidative desulfurization of fuel oil was investigated using a process consisting of oxidation and distillation steps. In the oxidation step, various organic carboxylic acid/H₂ O₂ systems, especially acetic acid/H₂ O₂, were used as oxidant. They oxidize both easy and refractory sulfur compounds and convert them into oxidized sulfur compounds. The oxidized sulfur compounds are finally removed from fuel oil by distillation in the presence of water. The sulfur content of fuel oil was decreased to levels as low as 20 ppm (up to 90%) in a short contact time, ambient temperature, and atmospheric pressure. The results showed that applying this process did not have any deleterious influence on the distillation characteristic, composition, and content of fuel oil that was examined. An artificial neural network, using back propagation (BP), was also utilized for modeling oxidative desulfuration process of fuel oil. The comparison between the output of ANN modeling and the experimental data showed satisfactory agreement.     

低硫重质船用燃料油生产方案研究

对如何低成本生产低硫重质船用燃料油(硫质量分数不大于0.5%)进行了深入研究。研究结果表明:以固定床渣油加氢-催化裂化(催化)为代表的企业,通过调合加氢重油、脱硫脱固催化油浆和催化重柴油进行生产;以加工低硫原油为代表的企业,通过调合低硫减压渣油、加氢催化柴油和脱固催化油浆进行生产。生产过程中,需充分关注渣油加氢装置的脱硫深度,催化油浆脱固以及低硫重质船用燃料油的调合、储存和运输等问题。采用两个价格体系进行经济效益测算,低硫重质船用燃料油生产方案的经济效益稍差,但新发布的退税政策可以降低负面影响,政策优惠将给国内炼化企业生产低硫重质船用燃料油带来新的发展机遇。     

A Comparative Study of the HDS Kinetics of Straight Run and Coker Gas Oils Under Deep Desulfurization Conditions

Abstract

Deep desulfurization of diesel blending streams has gained considerable importance in the petroleum refining industry in recent years due to environmental regulations which limit the sulfur content of diesel fuel to very low levels. Among the various factors influencing deep desulfurization of diesel to lower and lower sulfur levels, the quality of the feedstock plays an important role. In the present work, the degree of desulfurization of two different feedstocks, namely, coker gas oil (CGO) and straight run gas oil (SRGO) and their blends was investigated under different operating severities. The distributions of different types of sulfur compounds in both feeds were examined by GC-SCD. Kinetics of desulfurization of both feeds under deep desulfurization conditions was also studied. The results revealed that SRGO, in spite of having a significantly larger amount of total sulfur, desulfurized more easily and produced diesel fuel with low sulfur levels in the desired range (< 350 ppm) at lower temperatures compared with CGO. More severe operating conditions (higher temperature, lower LHSV etc.) were found necessary to bring about deep desulfurization of CGO and its blends with SRGO to the same sulfur level. Kinetic experiments showed a reaction order of 1.5 for the overall HDS of both types of feeds, but the activation energy was higher for CGO (30 kcal/mole) than SRGO (24 kcal/mole). The results are explained on the basis of the differences in the concentrations of nitrogen and refractory sulfur compounds present in the two feeds.     

Oxidative desulfurization using graphene and its composites for fuel containing thiophene and its derivatives: An update review

Oxidative desulfurization, in which the aromatic sulfur containing compounds are oxidized to their analogical sulfones and subsequently extracted, has assured to be one of the exceedingly effective desulfurization processes for resulting ultra-low sulfur import fuels. The oxidative desulfurization process using graphene oxide has attracted significant interest for sulfur removal from fuels. In this survey, we discussed systematically the techniques of desulfurizations in catalytic oxidation, including the role of graphene as a supported catalyst, the research results of oxidative desulfurization using graphene oxide and provided the factors affecting the desulfurization process. We also debate the challenges counterattack the use of graphene oxide in this view, including their preparation methods and their efficiency and stability as a supported catalyst. Also, there are some of the desulfurization processes currently under investigation such as oxidation, biodesulfurization, and adsorption was outlined in brief. The combustion of fossil fuels containing sulfur compounds emits some of the sulfur oxides which considered a harmful influence on human health and the surrounding environment as well as the economy. It can be concluded that GO remains a kind of ideal supported catalysts to recognize a pure fuel in the near futurity due to their eligible physicochemical characteristics.     

非加氢深度脱除燃料油中硫化物的研究进展

综述了非加氢深度脱除燃料油中硫化物的技术进展,主要包括吸附脱硫技术、萃取脱硫技术和氧化脱硫技术。吸附脱硫技术对硫化物的选择性较差,且很难达到深度脱硫目的;而萃取脱硫的溶剂选择较难,且萃取的硫化物类型较少以及溶剂回收较难,使得萃取脱硫技术难以实现工业化。氧化脱硫技术具有操作条件温和,操作费用低,脱硫率高,不产生二次污染等特点,尤其以钛硅分子筛为催化剂、双氧水为氧化剂对燃料油的氧化脱硫能达到较理想的效果,是近期最有希望实现工业化以及零硫目标的脱硫技术,但氧化剂的类型和催化剂还有待进一步改进。     

Oxidative Desulfurization of Fuel Oil: Modeling Based on Artificial Neural Network

Abstract

Oxidative desulfurization of fuel oil was investigated using a process consisting of oxidation and distillation steps. In the oxidation step, various organic carboxylic acid/H₂ O₂ systems, especially acetic acid/H₂ O₂, were used as oxidant. They oxidize both easy and refractory sulfur compounds and convert them into oxidized sulfur compounds. The oxidized sulfur compounds are finally removed from fuel oil by distillation in the presence of water. The sulfur content of fuel oil was decreased to levels as low as 20 ppm (up to 90%) in a short contact time, ambient temperature, and atmospheric pressure. The results showed that applying this process did not have any deleterious influence on the distillation characteristic, composition, and content of fuel oil that was examined. An artificial neural network, using back propagation (BP), was also utilized for modeling oxidative desulfuration process of fuel oil. The comparison between the output of ANN modeling and the experimental data showed satisfactory agreement.