柴油氧化脱硫技术研究进展

介绍了近年来柴油脱硫技术研究的进展情况,主委包括过氧化氢氧化脱硫、氧气催化氧化脱硫、超声波氧化脱硫和光化学氧化脱硫。分析了不河方法的优势及应用现状,与加氢脱硫技术相比,氧化脱硫将成为今后生产超低硫柴油的主要工艺之一。     

柴油氧化脱硫技术研究进展

柴油氧化脱硫技术具有工艺流程简单,操作条件温和、操作费用低等优点,已成为近年来国内外研究开发的热点,介绍了近年来柴油氧化脱硫技术的研究进展,分析了不同方法的优点和缺点,并提出柴油氧化脱硫技术未来的研究方向。     

柴油氧化脱硫技术的研究进展

介绍了柴油氧化脱硫机理及柴油氧化脱硫技术的最新进展。     

清洁柴油脱硫技术研究进展

随着世界各国对环保法规的日益关注,柴油脱硫技术在世界范围内被广泛研究,清洁柴油的生产已是超低硫燃料的发展趋势。目前柴油脱硫技术主要以加氢脱硫技术为主,但是近年来出现了许多新的脱硫技术,其中柴油非加氢脱硫技术的研究进展较快。综述了清洁柴油的脱硫技术并进行了展望。     

国内外柴油氧化脱硫技术研究进展

介绍了国内外柴油产品质量与标准的发展趋势,以及国内外柴油氧化脱硫技术的研究进展,各种柴油氧化脱硫技术的优势及存在的问题,与加氢脱硫技术相比,氧化脱硫将成为今后生产超低硫柴油的主要工艺之一。     

柴油脱硫技术与展望

随着世界清洁柴油中含硫标准的提高,降低柴油中硫含量已成为全球性关注的问题。近几年,出现了许多新的脱硫技术,其中柴油非加氢脱硫技术的研究进展较快。介绍了氧化脱硫和非氧化脱硫技术的理论基础,重点概述了这方面取得的最新成果,并从清洁生产的角度出发,对柴油脱硫技术的发展进行了展望。     

柴油脱硫技术研究进展

柴油低硫化及其含硫标准的日趋严格,是世界各国柴油产品质量与标准的发展趋势。综述了目前柴油脱硫技术（非加氢脱硫技术、加氢脱硫技术）的研究进展,并对其前景进行了展望。     

柴油氧化脱硫技术新进展

柴油低硫化及其含硫标准的日趋严格,是世界各国柴油产品质量与标准的发展趋势。加氢脱硫技术生产低硫柴油,存在投资大、操作费用高和操作条件苛刻的缺点,导致柴油成本大幅攀升,柴油氧化脱硫技术已成为研究热点。综述了国内外柴油氧化脱硫技术的研究进展,认为柴油氧化脱硫技术将成为今后生产超低硫清洁柴油的主要工艺之一。     

柴油氧化脱硫技术新进展

柴油低硫化及其含硫标准的日趋严格,是世界各国柴油产品质量与标准的发展趋势。加氢脱硫技术生产低硫柴油,存在投资大、操作费用高和操作条件苛刻的缺点,导致柴油成本大幅攀升,柴油氧化脱硫技术已成为研究热点。综述了国内外柴油氧化脱硫技术的研究进展,认为柴油氧化脱硫技术将成为今后生产超低硫清洁柴油的主要工艺之一。     

柴油氧化脱硫技术研究进展

介绍了近年来柴油氧化脱硫技术研究的进展情况,主要包括:H2O2均相、非均相催化氧化脱硫,超声波氧化脱硫,光催化氧化脱硫和分子氧直接氧化脱硫等。认为分子氧直接氧化脱硫技术克服了H2O2价格较高、稳定性差等缺点,并且该法具有操作条件缓和,反应时间短等优点,将成为柴油氧化脱硫的主要研究方向。     

A new method for obtaining ultra-low sulfur diesel fuel via ultrasound assisted oxidative desulfurization☆

Due to the requirement of stringent rules for ultra-low sulfur content of diesel fuels, it is necessary to develop alternative methods for desulfurization of fossil fuel derived oil. Using appropriate oxidants and catalysts with the assistance of ultrasound irradiation, model compounds such as dibenzothiophene can be quantitatively oxidized in minutes. For diesel fuels containing various levels of sulfur content, and through the use of catalytic oxidation and ultrasonication followed by solvent extraction, removal efficiency of sulfur-bearing compounds can reach or exceed 99% in a short contact time at ambient temperature and atmospheric pressure. This simple approach can be the basis for obtaining ultra-low sulfur-containing diesel oil. GC-PFPD, GC-MS, and GC-SIMDIS were used to monitor the change of organic sulfur compounds and hydrocarbons in diesels during the process.     

Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]₂ in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly.     

功率超声辅助下柴油氧化脱硫的研究

催化氧化脱硫是降低柴油硫含量的非加氢脱硫工艺,在催化氧化溶剂抽提的基础上,同时增加超声波为反应提供能量,开辟了一条全新的柴油氧化脱硫技术。考察了萃取剂的选择、萃取剂油比、萃取静置时间、萃取次数等对脱硫效果的影响。实验结果表明：在功率超声作用下,以H2O2为氧化剂,甲酸和磷酸为催化剂,氧化剂油比（体积比）=1：10,H2O2：催化剂（体积比）=1：1,反应温度50℃,反应时间10min时,萃取剂为DMF,萃取剂油比（体积比）=1：1,一次萃取20min,萃取次数2次为最佳。     

Study of diesel fuel desulfurization by adsorption

Removal of sulfur from diesel fuel by adsorption on a commercial activated carbon and 13X type zeolite was studied in a batch adsorber. Kinetic characterization of the adsorption process was performed applying Lagergren's pseudo-first order, pseudo-second order and intraparticle diffusion models using data collected during experiments carried out to determine the sulfur adsorption dependency on time. The experiments investigating adsorption efficiency regarding initial sulfur concentration were also performed and the results were fitted to Langmuir and Freundlich isotherms, respectively. Activated carbon Norit SXRO PLUS was found to have much better adsorption characteristics. The process of sulfur adsorption on the fore mentioned activated carbon was further studied by statistically analyzing data collected during experiments which were carried out according to three-factor two-level factorial design. Statistical analysis involved the calculation of effects of individual parameters and their interactions on sulfur adsorption and the development of statistical models of the process.     

氧化法脱除重油催化裂化柴油中的硫化物

采用双氧水-甲酸对重油催化裂化柴油进行氧化,然后使用N,N-二甲基甲酰胺萃取剂萃取脱硫。研究了在反应体系中氧化时间、氧化温度以及双氧水与甲酸的加入量对氧化脱硫率的影响,并考察了加入分散剂Span-80的效果。最终得到双氧水-甲酸-Span-80体系最佳氧化条件：分散剂Span-80为2.0%,双氧水为36%,甲酸为32%,氧化温度为60 ℃,氧化时间为50 min。分散剂Span-80的加入可以大大提高双氧水-甲酸体系对重油催化裂化柴油的氧化脱硫能力。在双氧水-甲酸体系最佳条件下氧化萃取脱硫率为85.58%,双氧水-甲酸-Span-80体系脱硫率高达98.27%,重油催化裂化柴油的硫含量由12 500 mg/L降至216 mg/L。气相色谱结果显示,氧化脱硫后重油催化裂化柴油中的噻吩、苯并噻吩及其衍生物基本被脱除,有少量二苯并噻吩及其衍生物需要进一步脱除。     

超声波技术在柴油氧化脱硫中的应用

介绍了超声波在H2O2-无机酸、H2O2-有机酸、H2O2-固体酸、Fenton试剂氧化柴油脱硫技术中的应用,其中超声波-Fenton试剂氧化脱硫效果较好,极有可能获得更广阔的工业化前景。Su lphCo已成功的应用超声波在相当低的温度和压力条件下使用一套5 000桶/d的可移动的超声裂化装置对柴油进行脱硫处理,该装置造价比新的高压加氢装置低50%,在柴油精制中应用该技术总成本也非常低。同时,对柴油超声波氧化脱硫技术的应用前景进行了展望。     

Deep desulfurization of diesel oil oxidized by Fe (VI) systems

Fe (VI) compound, such as K₂FeO₄, is a powerful oxidizing agent. Its oxidative potential is higher than KMnO₄, O₃ and Cl₂. Oxidation activity of Fe (VI) compounds can be adjusted by modifying their structure and pH value of media. The reduction of Fe (VI), differing from Cr and Mn, results in a relatively non-toxic by-product Fe (III) compounds, which suggests that Fe (VI) compound is an environmentally friendly oxidant. Oxidation of model sulfur compound and diesel oil by K₂FeO₄ in water-phase, in organic acid and in the presence of phase-transfer catalysts is investigated, respectively. The results show that the activity of oxidation of benzothiophene (BT) and dibenzothiophene (DBT) is low in water-phase, even adding phase-transfer catalyst to the system, because K₂FeO₄ reacts rapidly with water to form brown Fe(OH)₃ to lose ability of oxidation of organic sulfur compounds. The activity of oxidation of the BT and DBT increases markedly in acetic acid. Moreover, the addition of the solid catalyst to the acetic acid medium promotes very remarkably oxidation of organic sulfur compounds. Conversions of the DBT and BT are 98.4% and 70.1%, respectively, under the condition of room temperature, atmospheric pressure, acetic acid/oil (v/v) = 1.0, K₂FeO₄/S (mol/mol) = 1.0 and catalyst/K₂FeO₄ (mol/mol) = 1.0. Under the same condition, diesel oil is oxidized, followed by furfural extraction, the results display sulfur removal rate is 96.7% and sulfur content in diesel oil reduces from 457 ppm to 15.1 ppm.     

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO_x) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol.     

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).