A REVIEW OF NON-CONVENTIONAL METHODS FOR THE DESULFURIZATION OF RESIDUAL FUEL OIL

ABSTRACT

Sulfur removal from residual fuel oil has received increasing attention in recent years mainly for the preparation of clean feedstocks for downstream conversion units and to meet the new specifications for petroleum products. This review presents discussion of non-conventional methods of fuel oil desulfurization other than hydrodesulfurization (HDS). These methods include oxidation, electrochemical, sodium, alkali, chemical treatment, and biodesulfurization.     

残渣型船用燃料油在线调合工艺及小试装置实验研究

针对船用残渣型燃料油在线调合工艺要求,开发了船用燃料油连续调合管理系统,设计了新型高效静态混合器,并在此基础上开发了残渣型燃料油连续调合工艺。建立了处理能力为240 L/h的残渣船用燃料油在线调合小试装置。运行实验表明,该设备运行平稳,能够实现调合方案生成、连续生产自动控制、产品性能实时反馈的全过程,可生产符合国标的船用残渣型燃料油,产品稳定性好。     

燃油活性炭吸附深度脱硫的机理及研究进展

吸附法深度脱硫可以在常温常压下选择性脱除燃油中的含硫有机化合物,是一种很有应用前景的技术.在归纳燃油组成及硫的类型的基础上,介绍了国内外燃油活性炭吸附深度脱硫机理的研究进展,包括分子尺寸选择机理、酸性位吸附机理、络合吸附机理和催化氧化机理及其影响因素;同时对吸附脱硫工艺的研究前景进行了展望.     

用于残渣燃料油的聚醚羧酸型沥青分散剂合成与评价

针对调配的残渣燃料油在使用过程中出现的沥青质组分聚集沉淀的问题,制备了一种烷基酚聚氧乙烯醚羧酸沥青分散剂,并通过红外光谱确证了聚醚羧酸产物的化学结构.实验结果表明,目标产物的较佳合成条件为:n(NP-4):n(CEA):n(NaOH)=1:2:3、反应温度45℃,反应时间4 h,n(丙酮):n(NP-4)=6:1,在该条件下,产物产率可达到86.2％.结合沥青质分子结构模型,分析了该聚醚羧酸型沥青分散剂的作用机理.总潜在沉淀物(热过滤法)测定试验表明,添加该剂0.3％(质量分数)的燃料油总潜在沉淀物降至0.05％ 以下,相应的沥青分散率达到99％ 以上,显示出良好的防沥青沉积性能.     

轻质燃料油硫含量分析方法评价

对轻质燃料油硫含量分析所使用的紫外荧光法、单波长色散X射线荧光光谱法、电量法3种方法进行评价,就其影响因素及3种分析方法的一致性进行比对分析。结果表明,3种分析方法测定低硫含量样品分析结果基本一致,重复性好、准确度高。同时对不同分析方法的优缺点进行了比较,在硫含量分析方法的选择时,可根据馏分情况、硫含量及实验室设备情况等因素来选择准确、高效、经济的检测方法。     

燃料油脱硫技术进展及发展趋势

综述了国内外现有燃料油脱硫技术的研究进展,并结合其研究或应用的实际特点及目前燃料油脱硫技术研究存在的问题,探讨了今后燃料油脱硫技术的发展方向。强调在现有以催化加氢脱硫技术为主的基础上,开发可降硫的催化剂和添加剂(助剂)以及生物脱硫、萃取脱硫、吸附脱硫、络合脱硫等技术。     

多产中间馏分油的渣油裂化催化剂MLC—500的开发

开发了一种能裂解重质原料油、多产中间馏分油的裂化催化剂ＭＬＣ－５００。通过对超稳Ｙ型分子筛进行酸性调整,获得了拥有适当酸性中心数和酸强度分布的改性Ｙ型分子筛;经一定的物理化学过程,使大孔载体具有梯度孔径分布。因此,对不同性质的原料油,可有效地调整ＭＬＣ－５００的物理化学性质,获得理想的产品分布。在沧州炼油厂进行的多产柴油工业应用试验表明,ＭＬＣ－５００比对比剂的柴汽比提高０．１０,轻油收率增加０．３３个百分点,总液体收率增加１．５个百分点,获得了较高的中间馏分油收率。     

低黏度汽油机油燃油经济性测试方法区分性研究

随着现行节能和排放法规的日益严格,机油节能越来越受到汽车厂商的重视.GF-6汽油机油规格对机油节能提出较高要求,使用一种台架来评定用于多种发动机的润滑油的节能性能并不具备广泛的代表性,因此针对特定的某型号4缸发动机建立了一套能准确评价汽油机油节能的评定方法,并开展台架试验,将台架试验结果与SRV模拟试验考察汽油机油摩擦...     

分子筛吸附脱硫生产清洁燃料

分子筛吸附脱硫技术因具有投资成本低、操作条件温和、脱硫率高等优点而备受关注。本文综述了分子筛吸附脱硫领域的最新研究成果,着重介绍了改性分子筛的吸附性能与分子筛的再生性能,并对分子筛吸附脱硫的进一步研究进行了展望。     

发展重油加工提高轻质产品收率

由于发动机燃料需求量增长、更为严格的环保要求和质量控制以及重质原油开采量的增加，发展重油加工，增加轻质石油产品，已成为世界炼油工业的重大问题。重油加工方案的研究表明：延迟焦化和催化裂化的组合工艺有较高的效益，而重油加氢裂化和重油催化裂化的组合工艺，可以把高含硫重油最大量地转化为轻质产品。重油催化裂化、延迟焦化和催化裂化、重油加氢裂化和重油催化裂化组合工艺是我国本世纪内重油加工发展的重点。发展重油加氢裂化近期以固定床加氢裂化为宜。     

大豆油作为柴油机燃料的试验研究

为考察植物油在柴油发动机中的使用性能,将植物油（以市售大豆油为例）和-10号军用柴油按照不同的比例掺兑,进行了植物油和柴油实验室理化性能试验对比分析、发动机特性试验考察、实车实际性能试验验证。结果表明植物油使WD615柴油机综合性能较好,可以作为柴油机燃料使用。     

烟气脱硫工艺进展综述

燃煤烟气中的SO2是大气的主要污染源,减少SO2污染成为当今大气环境治理的当务之急。介绍了常见的干法和湿法脱硫工艺的特点,概述了其它烟气脱硫技术的最新发展,并对脱硫技术今后的发展提出了展望。     

柴油氧化萃取脱硫工艺研究

以过氧化氢为氧化剂，甲酸为氧化反应的催化剂，甲醇为萃取剂，对柴油选择性氧化萃取法脱硫技术的工艺条件进行了研究。实验结果表明，在O与S摩尔比为10，氧化时间为40min，氧化温度为70℃，萃取剂为甲醇，剂油比为1．0，萃取时间为30min，萃取温度为室温的最佳工艺条件下，一级萃取柴油的脱硫率为78．2％；三级萃取柴油的脱硫率为97．7％，柴油硫含量为18μg／g，小于50μg／g，达到欧Ⅳ排放标准的要求。     

蒸汽驱残余油饱和度的简易确定方法

本文提出了一种简易实用的计算热驱残余油饱和度方法。该方法主要将实验室热驱结果和柏授—皮特曼关系相结合,在溫度、原油粘度、油藏物性条件与残余油饱和度间建立关系,以求得蒸汽驱残余油饱和度值。该方法应用于克拉玛依油田六区、九区和红山嘴地区、风城地区,其计算结果与有关研究成果基本一致,计算出的蒸汽驱残余油饱和度值可作为稠油热采可采储量、数值模拟及编制开发方案的参数。     

热加工过程中渣油结焦倾向的评价方法

渣油缩合反应是导致延迟焦化加热炉炉管结焦的根本原因，而缩合产物与原料性质和反应条件有关。提出了用不同油样在相同反应条件下得到的结焦因子作为评价油样结焦倾向的方法。在考察反应温度和反应时间对缩合产物影响的基础上确定了测定结焦因子的实验条件。利用研制的静态实验仪器对国内主要油源的减压渣油的结焦因子进行了测定，重复性偏差、非控制偏差分析结果表明实验结果是可靠的。     

模拟轻质油品烷基化沉淀法脱硫

 以精制油品为溶剂,苯并噻吩(BT)、二苯并噻吩(DBT)、4,6—二甲基二苯并噻吩(4,6—DMDBT)作为模型含硫化合物组成模拟轻质油品,以卤代烃和四氟化硼钾为烷基化剂对模拟轻质油品烷基化沉淀脱硫进行了研究。考察了反应温度、反应时间、烷基化剂种类及其用量、溶剂等因素对总硫脱除的影响。实验结果表明：在反应温度30℃,CH3CH2Br：S=80：1(mol/mol),KBF4：S=30:1(mol/mol),反应时间在24h的条件下,总硫脱除率可以达到76.5%。     

喷气燃料冰点的测定方法

综述国内外喷气燃料冰点测定方法的进展、原理及国内相应标准化接轨的情况。美国喷气燃料标准ASTM D1655-07e规定可以采用标准试验方法ASTM D2386-06、自动相转移法ASTM D5972-05、自动激光法ASTM D7153-05、自动光纤法ASTM D7154-05等4种方法中的任何一种测定喷气燃料冰点,且规定ASTM D5972-05、ASTM D7153-05为仲裁方法;国外其它主要国家的喷气燃料标准也允许使用这些冰点的测定方法,但规定只有ASTM D2386-06或其等效标准为仲裁方法;中国3号喷气燃料标准GB6537—2006规定采用标准试验方法GB/T 2430-2008和相转移法SH/T 0770-2005测定喷气燃料冰点,指定GB/T 2430-2008为仲裁方法。ASTM D5972-05,ASTM D7153-05,ASTM D7154-05为近年来新发展的仪器分析方法,自动化程度较高,测定重复性好。另外还简单介绍了一些正在研究但没有标准化的喷气燃料冰点的测定方法。     

THE IMPORTANCE OF PYROLYSIS IN DIESEL IGNITION OF RESIDUAL FUEL OILS

Recent attempts to increase yields of distillate fuels from crude oil have resulted in a decline in the ignition quality of residual fuel oils and claims of ignition problems in large marine Diesel engines. This has revived an interest in fundamental studies of the ignition of liquid fuels and in new ways of defining and measuring ignition quality.

As part of an extensive study of the ignition of a range of residual fuels oils and during the development of novel teats of ignition quality it became obvious that thermal cracking of the fuel could play an important part in the pre-ignition chemistry. This paper reports kinetic data from simple experiments performed on the pyrolyses of residual fuel oils. Small samples and high heating rates were used to try to match the conditions inside a Blow-speed Diesel engine. This data has been used to assess the contribution that thermal cracking makes to ignition processes.

Pyrolyses were carried out on a small silica-coated platinum coil in the inlet of a gas chromatograph. Light hydrocarbon pyrolysis products were formed, and the extent and rate of cracking determined at four temperatures.

Assuming that reaction took place on a surface surrounding the oil and that a constant supply of reactants were available, pseudo zero order rate constants for the initial part of the reaction were evaluated. They showed an Arrhenius relationship with temperature giving an overall apparent activation energy of 110 kJ mol^-1. Extrapolating rate constants to temperatures expected in Diesel engines, and assuming typical droplet sizes end ignition delays, it was shown that thermal cracking of fuels was possible before ignition and that it is likely that these reactions will have a strong influence on the processes leading to ignition. It was also shown that the presence of oxygen greatly increases the rate of thermal cracking.     

THE IMPORTANCE OF PYROLYSIS IN DIESEL IGNITION OF RESIDUAL FUEL OILS

ABSTRACT

Recent attempts to increase yields of distillate fuels from crude oil have resulted in a decline in the ignition quality of residual fuel oils and claims of ignition problems in large marine Diesel engines. This has revived an interest in fundamental studies of the ignition of liquid fuels and in new ways of defining and measuring ignition quality.

As part of an extensive study of the ignition of a range of residual fuels oils and during the development of novel teats of ignition quality it became obvious that thermal cracking of the fuel could play an important part in the pre-ignition chemistry. This paper reports kinetic data from simple experiments performed on the pyrolyses of residual fuel oils. Small samples and high heating rates were used to try to match the conditions inside a Blow-speed Diesel engine. This data has been used to assess the contribution that thermal cracking makes to ignition processes.

Pyrolyses were carried out on a small silica-coated platinum coil in the inlet of a gas chromatograph. Light hydrocarbon pyrolysis products were formed, and the extent and rate of cracking determined at four temperatures.

Assuming that reaction took place on a surface surrounding the oil and that a constant supply of reactants were available, pseudo zero order rate constants for the initial part of the reaction were evaluated. They showed an Arrhenius relationship with temperature giving an overall apparent activation energy of 110 kJ mol^-1. Extrapolating rate constants to temperatures expected in Diesel engines, and assuming typical droplet sizes end ignition delays, it was shown that thermal cracking of fuels was possible before ignition and that it is likely that these reactions will have a strong influence on the processes leading to ignition. It was also shown that the presence of oxygen greatly increases the rate of thermal cracking.     

燃料油纳米添加剂的制备及性能研究

在实验室用脂肪酸对3种纳米微粒进行了有效修饰,并对修饰后的纳米微粒进行了结构表征及在油中的分散性试验。结果表明,纳米微粒经表面修饰后在油中的分散稳定性得到显著提高。采用氧弹热值对比法对所研制的纳米添加剂进行了实验室评价,结果表明,修饰纳米微粒DML2,DML3均能在不同程度上改善燃料油的燃烧性能。当DML2添加量为1-10μg/g时,锅炉燃料油的燃烧效率可提高2.9-3.2个百分点,残余物减少22.3％-26.2％。