催化裂化柴油氧化萃取脱硫工艺研究

以氧气作氧化剂,甲酸作催化剂,N-甲基吡咯烷酮（NMP）作萃取剂,采用催化氧化反应与溶剂萃取相结合的方法对催化裂化柴油进行了氧化萃取脱硫实验。通过单因素实验考察了催化剂用量,催化氧化温度、时间、氧气压力及萃取剂的用量等对催化裂化柴油硫含量的影响。通过实验得出最适宜的脱硫条件为：反应温度80℃;反应时间90min;充氧压力0．6MPa;催化剂体积分数为10％。经催化氧化,柴油硫质量分数可从1694．2μg/g降到190．8μg/g,脱硫率达到88．7％;在剂油比为1．0和室温条件下,用NMP三级萃取,柴油硫质量分数为37．5μg/g,小于50μg/g,达到欧Ⅳ排放标准的要求。     

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.     

Study on Modified Y Zeolites and Their Behaviors in Selective Adsorptive Desulfurization of FCC Gasoline(Ⅰ)

Na Y zeolite was modified through dealumination with oxalic acid,and the HY zeolite was obtained by calcination of the modified NaY zeolite.The zeolite molding process was carried out at ambient temperature(25℃),and the influence of solid/fuel mass ratio and adsorptive desulfurization time on the HY zeolite were investigated through tests on static selective adsorptive desulfurization of FCC gasoline containing organic sulfur compounds(with a S content=135 ppm).The sulfur content and sulphide types in the FCC gasoline were analyzed by a GC 2010 sulfur analyzer and a GC-SCD chromatograph.The test results showed that the molded HY zeolite was better than the unmolded HY zeolite.At a static adsorptive desulfurization time on the molded HY zeolite equating to 6 hours,a solid/fuel mass ratio of 1:3,the sulfur content of FCC gasoline was decreased to 30 ppm,and the desulfurization rate was equal to 78%.When the breakthrough point of the molded HY was equal to 50 ppm,the molded HY zeolite was capable of adsorbing 4.86 mg of sulfur per gram of adsorbent.And the regeneration rate of molded HY zeolite was equal to 98%.     

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.     

Oxidative desulfurization of straight-run diesel fraction on vanadium–molybdenum catalysts

It has been shown that the most appropriate and simple process for desulfurization of motor fuels is the direct oxidation of sulfur compounds with atmospheric oxygen on heterogeneous catalysts based on transition metal oxides. The feasibility of oxidation of thiophene with atmospheric oxygen in a model mixture with dodecane over vanadium–molybdenum catalysts has been shown, as well as that of oxidative desulfurization of actual straight-run diesel fraction. The activity of a number of samples of oxidative of desulfurization catalysts has been examined, the composition of the most effective catalyst has been determined, and optimum process conditions have been found.     

Fabrication of oxygen-defective tungsten oxide nanorods for deep oxidative desulfurization of fuel

Owing to the increasingly serious environmental issues caused by the sulfur burnt in fuel, desulfurization has become an important topic. In this work, an amphiphilic oxygen-defective tungsten oxide was synthesized by a colloidal chemistry method. The amphiphilic property and oxygen defects were well characterized, and the structure of the oxygen-defective tungsten oxide catalyst was investigated. In addition, the catalyst was employed in oxidative desulfurization system of fuel, and deep desulfurization was achieved. It was found that the very high oxidative desulfurization performance of oxygen-defective tungsten oxide catalyst resulted from both the amphiphilic property and oxygen defects. This work can provide a strategy for preparation of highly active metal oxide catalysts with oxygen defects in oxidative desulfurization reaction of fuel.     

Peroxide oxidative desulfurization of a mixture of nonhydrotreated vacuum gas oil and diesel fraction

Oxidative desulfurization of a model mixture on the basis of vacuum gas oil and diesel fuel by hydrogen peroxide in the presence of formic acid has been studied. A technology of a two-phase system with a phase-transfer catalyst has been employed for the desulfurization. The optimum reaction time is 6 h and the hydrogen peroxide: sulfur molar ratio is 4: 1. As a result of successive triple oxidative desulfurization, 90% of total sulfur is removed from the model mixture.     

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.     

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。     

A Survey of Novel Processes to Produce Ultra Low Sulfur Gasoline

The restriction on sulfur level in gasoline has been increasingly tightened. The U.S.Tier Ⅱ regulation requires a reduction from average 340ppm to 30ppm from 2004 to 2008. Recently significant progress has been made in effective high sulfur removal, such as post treatment of FCC gasoline by selective hydrotreating, S Zorb sulfur removal technology, OATS process etc. The sulfur content of FCC gasoline can be deceased to less than 10ppm. With regard to gasoline pool composition in China, it is very important to look for effective desulfurization processes that are simple, straightforward, with less hydrogen consumption. Post-treatment of FCC gasoline is a preferred option. From the point of view of comprehensive utilization, alkylation, polymerization, isomerisation etc. can be added to desulfurization process to meet the requirement of ultra low sulfur, premium.     

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.     

Ultrasound assisted photocatalytic oxidative desulfurization of model diesel fuel

Ultrasound assisted photocatalytic oxidation technology is an efficient and gentle technology to remove the organic sulfur from diesel. The influence parameters of catalytic oxidation phase include catalyst dosage, reaction temperature, oxidation time, hydrogen peroxide to diesel fuel ratio and time of the extraction process. Furthermore, the comparison of the results under two conditions of ultrasound irradiation and mechanical agitation are also specially examined. The obtained results indicate that under the optimal condition, ultrasound assisted oxidative desulfurization (UAOD) is more efficient for sulfur removal which the desulfurization degree can be reached 99.47%.     

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...     

A Novel Technology for Desulfurization of FCC Diesel Fuels: Combination of Hydrogenation and Oxidation-assisted Ultrasound

Abstract

This new route that integrates with hydrodesulfurization (HDS) and ultra-sound-assisted oxidation desulfurization (UAODS) technology can be studied to decrease the sulfur content of high sulfuric FCC diesel fuel. In the integrating technology, the conventional HDS unit continues to produce below 500 μg/g hydrotreated diesel fuels, with UAODS unit used to make sulfur content below 50 μg/g, or even below 10 μg/g of diesel fuels. Since it has been discovered that cavitation can be originated from ultrasonic irradiation in water, ultrasound is an increasingly used tool to enhance chemical process rate. The addition of Fenton's reagent can enhance the sono-oxidative desulfurization efficiency for diesel fuels. UAODS has more advantages in removing thiophene and alkyl-thiophenes that are less reactive than other organosulfur species present in these hydrocarbon streams (e.g., alkyl sulfides, mercaptans) using HDS technology. The key to success is that the oxidative desulfurization process must be cost-effective versus the HDS revamp alternative available to refiners.     

三元低共熔溶剂促进球磨后高硫石油焦氧化脱硫

为实现高硫石油焦的有效脱硫使其“变废为宝”,本研究提出了一种基于机械球磨的高硫石油焦氧化脱硫新方法。首先使用球磨技术对高硫石油焦进行预处理,以增加石油焦的比表面积,暴露更多硫参与氧化。实验结果表明：与氧化钙共球磨后石油焦比表面积增加了8倍以上;在高硫石油焦球磨预处理的基础上,以苯磺酸基三元低共熔溶剂(DES)为反应溶剂及催化剂,30%双氧水(H₂O₂)为氧化剂,在70℃的温和条件下成功实现高硫石油焦的氧化脱硫,其硫质量分数可从4.46%降至2.09%。通过X射线衍射(XRD)、拉曼光谱(Raman)及扫描电子显微镜(SEM)探究了石油焦球磨及氧化脱硫前后结构的变化。通过傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)以及XRD分析了石油焦中硫的转化。通过电子自旋共振(ESR)试验证实了苯磺酸基三元DES的催化作用。     

惠州炼化分公司汽油质量升级

中海石油炼化有限责任公司惠州炼化分公司采用全馏分催化汽油选择性加氢脱硫工艺技术（CDOS-FRCN）新建了一套500 kt/a催化汽油加氢脱硫装置,能将催化汽油中硫的质量分数从336 μg/g降至11 μg/g,辛烷值损失1.4单位.装置投产前,主要生产满足国Ⅲ标准的汽油产品（硫质量分数不大于150 μg/g）;装置投产后,目前主要生产满足国Ⅳ标准的汽油产品（硫质量分数不大于50 μg/g）.通过调整装置的反应深度,能够全部生产符合国V标准的汽油产品（硫质量分数不大于10μg/g）,成功实现了汽油的质量升级,为社会提供清洁汽油产品.     

Diesel desulfurization using a ultrasound-assisted oxidative process

In this study, the removal of sulfur compounds from diesel samples using ultrasound-assisted oxidative desulfurization (UAODS) process in presence of different types of oxidizing agents was studied. Experiments were performed to assess the effects of influential parameters on the performance of UAODS process including ultrasonic irradiation time, oxidant type, mass ratio of oxidant to diesel fuel (oxidant: diesel), and finally acetic acid as an oxidative promoter. The efficiency of sulfur compounds removal from the diesel fuel dramatically improved using appropriate oxidative process with the assistance of ultrasound irradiation. H₂O₂ was found to be the most promising oxidant component whose concentration in the media directly affected total sulfur removal and thiol group conversion efficiencies. Using 4 wt% of H₂O₂ followed by 15 min of ultrasonic irradiation leaded to sulfur removal efficiency of 76% and thiol group conversion of 79% at ambient temperature and atmospheric pressure. Using acid acetic as the promoter of H₂O₂ also leaded to further sulfur compounds removal.     

Application of Microwave Technology for Desulfurization of Diesel Fuel

The microwave technology was introduced for the desulfurization of diesel fuel. The atmospheric second side-cut diesel fraction, which was supplied by Liaohe Petrochemical Company, was desulfurized by an oxidation process under microwave irradiation. Hydrogen peroxide (H202), can oxidize the sulfur compounds in diesel fuel selectively and convert them into sulfones. Based on the rule of dissolution by similar substances,these sulfones are removed from diesel fuel because they could be dissolved in solvent phase. So the sulfur content of diesel fuel is decreased. The influence of the concentration of oxidizing reagent, solvent phase to oil phase volume ratio (S/O), irradiation pressure, irradiation time, and the irradiation power have been investigated.The optimum conditions for the refining process was determined. The sulfur removal rate was 59.7% under the optimum conditions of 8%H2O2, S/O=0.25, 0.05MPa, 6 min, and 375W, respectively. When no microwave irradiation was applied, the removal rate was 11.5% only.     

Hydrogen peroxide oxidative desulfurization of model diesel mixtures using azacrown ethers

Hydrogen peroxide oxidative desulfurization of model diesel fuel mixtures in the presence of azacrown ethers and their complexes with niobium pentachloride at 40–80°C has been studied. It has been found that the use of complexes of azacrown ethers with NbCl₅ leads to a decrease in the total sulfur content in the model mixtures to 13% of the initial amount. The structure of the azacrown ether used has little effect on the extent of desulfurization of the model mixture.     

活性炭负载S2O8 2-/ZrO2催化剂的制备及其催化氧化脱硫性能

采用浸渍沉淀法制备了固体超强酸S2O2-8/ZrO2 AC催化剂,以二苯并噻吩(DBT)的正十二烷溶液为含硫化合物模拟油(硫质量分数为400 μg/g),H2O2为氧化剂,考察催化剂的催化氧化脱硫性能,采用BET、XRD、FT IR和NH3 TPD分析手段对其结构进行了表征。利用所制备的催化剂,考察了反应温度、反应时间、氧化剂用量、催化剂用量和乳化剂Span60用量对脱硫效果的影响。结果表明,当活性组分ZrO2负载量(质量分数)为10%,焙烧温度为650℃,所制备的S2O2-8/ZrO2 AC催化剂的催化氧化脱硫活性最高;其氧化20 mL模拟油的最佳操作条件为反应温度60℃、反应时间60 min、氧化剂/硫摩尔比5、乳化剂Span60用量01g,催化剂用量以每1 mL模拟油添加004 g计。在此条件下,DBT基本全部转化为相应的砜,采用N,N 二甲基甲酰胺(DMF)萃取,DMF/汽油体积比为1/4时,模拟油的脱硫率可以达到976%,回收率为925%,并且催化剂具有较好的稳定性。