微波作用下柴油脱硫新方法的研究

用φ(H2O2)=30%-HCOOH为氧化剂,N,N-二甲基甲酰胺(DMF)为萃取剂,采用微波辐射对柴油进行氧化脱硫,实验结果表明,在微波辐射压力为0.5MPa,微波功率为450W,恒压辐射时间为10min,氧化剂与油的体积比为1∶10,萃取剂与油的体积比为3∶4,萃取时间为15min的条件下,脱硫率可达到95.8%,收率达99.5%。     

微波辐射脱除柴油中碱性氮化物实验研究

提出以质量分数95％的乙醇为萃取剂,采用微波辐射脱除柴油中碱性氯化物的新方法,实验考察了微波辐射功率、辐射时间、压力、剂油比对脱氮效果的影响。结果表明,在功率为412．5 W,辐射时间为6min,压力为0．5 MPa,剂油体积比为0．5时碱性氮脱除率可达58．6％。该方法与传统实验方法相比工艺简单、反应时间短、清洁无污染。     

微波辐射催化裂化柴油脱硫工艺研究

介绍了以过氧化氢-甲酸为氧化剂对催化裂化(FCC)柴油进行微波辐射氧化脱硫,采用正交设计和单因素方法分别考察了微波辐射压力、辐射功率、恒压时间、萃取剂与油的体积比以及复合剂油的体积比对氧化脱硫反应的影响。得出最佳的实验条件:辐射压力0.4 MPa,恒压时间6 min,辐射功率412.5 W,复合溶剂用量为柴油用量的0.08倍,萃取剂油体积比1.5。在此条件下,硫的质量分数由5538.2μg/g降至825.2μg/g,回收率达到95%以上。     

焦化柴油过氧化环己酮氧化脱硫工艺研究

为了满足日趋严格的环保标准及市场对低硫柴油的巨大需求,柴油氧化脱硫技术显得日益重要。实验采用氧化萃取相结合的方法对焦化柴油进行了氧化脱硫实验。以自制过氧化环己酮为脱硫氧化剂,分别考察了氧化剂用量、氧化温度、氧化时间、萃取剂用量和二次萃取对焦化柴油硫含量的影响。结果表明,反应温度为100℃,反应时间3h,氧化剂与柴油的体积比0．04,萃取剂氮一甲基吡咯烷酮与柴油的剂油比为0．5,一级萃取可以脱除焦化柴油中93％的硫化物,柴油回收率达99％。二级萃取,可以脱除焦化柴油中95％的硫化物,柴油回收率为94．5％,硫含量可达到43．6μg·g^-1,小于50μg·g^-1,满足欧Ⅳ标准。     

微波辐射脱除催化裂化柴油中碱性氮化物研究

在微波辐射的条件下,用乙酸-w(乙醇)=95%络合萃取催化裂化柴油中碱性氮化物,考察了剂油体积比、乙酸加入量、微波辐射功率、辐射时间、辐射压力等工艺条件对碱性氮化物脱除率和柴油回收率的影响。结果表明:在剂油体积比1.0、乙酸与95%乙醇体积比0.05、辐射压力0.5 MPa、恒压辐射时间10 min、微波功率375 W最佳反应条件下,碱性氮化物脱除率82.4%,柴油回收率90.1%,较无微波辐射的条件下,碱性氮化物脱除率显著提高。     

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。     

柴油氧化萃取脱硫工艺

以固载磷钼酸的半焦为催化剂,span-85为乳化剂,双氧水为氧化剂、,对流化催化裂化(FCC)柴油进行氧化脱硫,分别考察了不同剂油比、反应时间和反应温度对脱硫率的影响.得到合适的脱硫工艺条件:反应时间60min、反应温度60℃、剂油比为1:40.在此条件下,FCC柴油中的硫含量由1 400 μg/g降至150μg/g,脱硫率达到89%.     

超声波作用下柴油氧化脱硫工艺研究

对超声作用下柴油氧化脱硫进行了研究,采用H2O2作为此工艺的氧化剂.通过对不同浓度的H2O2对河南南阳催化裂化柴油脱硫效果考察发现,30%浓度的H2O2的脱硫率最高.同时无机酸催化剂的脱硫效果表明,硫酸和磷酸按1∶1比例混合效果最好.再加入金属催化剂后脱硫率更高.实验结果表明了,功率超声作用下,H2O2-硫酸与磷酸1/1混合酸体系的最优操作条件:氧化体系∶油(体积比)=3∶10;H2O2∶混合酸(体积比)=1∶1;超声作用时间9min.萃取剂:DMF;萃取剂∶油(体积比)=1∶1;萃取一次.硫含量从1936.48μg/g降到99.73μg/g,脱硫率94.8%,油收率90.2%.可见功率超声强化了整个氧化脱硫过程.此外,在相同的氧化和萃取条件下,柴油在低频28kHz时的脱硫效果比40kHz的脱硫效果好;同时在功率超声的功率为200W时脱硫率最大.     

超声条件下柴油氧化脱硫的研究

采用H2O2-甲酸作为氧化剂将催化裂化柴油中的硫化物（主要为苯并噻吩类）氧化成相应的砜,同时引入超声波为反应提供能量,考察（油/剂）比、氧化温度、反应时间、萃取静置时间、（萃取剂/油）比和萃取次数等因素对脱硫效果的影响。在适宜条件下,脱硫率可达94.2%,收率可达90%以上。     

微波辐射合成苯甲酸

以苯甲醛为原料,KMnO4为氧化剂,在微波辐射下相转移催化合成了苯甲酸。讨论了微波功率、辐射时间、催化剂等条件对反应的影响,实验结果表明,反应的最佳条件为：苯甲醛0．04mol,微波功率750W,辐射时间10min,四丁基溴化铵1．0g,碳酸钠4．0g,高锰酸钾42g,产率可达77.9％。     

Microwave-assisted extractive catalytic-oxidative desulfurization of diesel fuel via a VO(acac)2/ionic liquid system with H2O2 and H2SO4 as oxidizing agents

The removal of sulfur compounds from transportation fuel is an important aspect for protecting environment and for fuel cell applications. On the other hand, an innovative way to remove the sulfur is necessary because clean low-sulfur diesel is more widely used in the world today. In this work, we studied the effect of microwave irradiation power and time on the extractive catalytic oxidative desulfurization (ECODS) process of diesel fuel model (40 mL with initial S-content of 450 ppm), using vanadyl acetylacetonate (VO(acac)₂) as a catalyst and N-carboxymethylpyridine hydrosulphate ionic liquid ([CH₂COOHPy][HSO₄] IL) as an extractant, and hydrogen peroxide (H₂O₂) as an oxidant agent. The optimal microwave-assisted extractive catalytic – oxidative desulfurization (MECODS) experimental conditions were as follows: microwave irradiation power?=?500?W, microwave irradiation time?=?90?s, IL/diesel volume ratio?=?1:10, VO(acaca)₂/diesel mass ratio?=?0.5?wt%, and H₂O₂ volume?=?1 mL. Under these conditions, the sulfur content in commercial diesel fuel was reduced from 450 to 60?ppm (sulfur removal efficiency of 86.67%), which was superior to that of the simple oxidation with no IL (22.6%) or oxidation with not including catalyst (11.3%), and without affecting the physicochemical properties of diesel fuel. The catalytic system VO(acac)₂/IL can be recycled 5 times with merely a negligible loss in activity. Based on these experimental results, a MECODS mechanism was proposed. Ultra-deep desulfurization with 99.1% of sulfur removal efficiency was reached, using MECODS reaction under optimum conditions by adding 3?mL of H₂SO₄ (0.1?N) to the main reaction. This highest sulfur removal efficiency can be attributed to the synergetic effect between microwave activation heating energy and the additional protonation, which multiplied the sulfones’ (BTO₂s and DBTO₂s) formation pathways and thus accelerated the desulfurization reactions.     

FCC柴油氧气氧化萃取法脱硫研究

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质量分数的影响。通过实验得出最适宜的脱硫条件为:反应温度80℃,反应时间90 min,充氧压力0.6 MPa,V(催化剂)∶V(柴油)=10%。经催化氧化,柴油硫质量分数可从1 694.2μg/g降到190.8μg/g,脱硫率达到88.7%;在V(萃取剂)∶V(柴油)=1.0和室温条件下,用NMP萃取3次,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 Hydrocarbon Fuels

New requirements for very low sulfur content (10 ppm) in liquid motor fuels demand novel approaches for ultra-deep desulfurization. For production of near-zero-sulfur diesel and low-sulfur fuel oil, removal of refractory sulfur compounds, like 4,6-dimethyldibenzothiophene and other alkyl-substituted thiophene derivatives, is necessary. Elimination of these compounds by hydrodesulfurization (HDS) requires high hydrogen consumption, high pressure equipment, and new catalysts. Various oxidative desulfurization processes, including recent advances in this field for diesel fuels, and the drawbacks of this technology in comparison with HDS are examined and discussed. It is shown that the oxidation of sulfur compounds to sulfones with hydrogen peroxide allows for production of diesel fuels with a sulfur content of 10 ppmw or lower at atmospheric pressure and room temperature. The gas phase oxidative desulfurization of sulfur compounds with air or oxygen is feasible at atmospheric pressure and higher temperatures: 90–300 °С and offers better economic solutions and incentives.     

柴油氧化吸附脱硫工艺的研究

以过氧化氢为氧化剂,甲酸为催化剂,Al2O3为吸附剂,研究柴油氧化吸附脱硫工艺条件。实验结果表明,在n（氧）∶n（硫）=10.0,氧化时间为40min,氧化温度为70℃,V（吸附剂）∶V（油）=1∶5.5,吸附时间为30min,吸附温度为40℃时,吸附柴油的脱硫率为97.32%,柴油w（硫）=20.5μg/g,达到欧洲Ⅳ柴油标准：w（总硫）〈50μg/g。     

柴油氧化脱硫技术的研究

通过H2O2/HCOOH体系对柴油选择性氧化脱硫技术的研究。考察了H2O2/HCOOH体系反应温度、反应时间、剂油比等因素对氧化脱硫效果的影响。实验结果表明,温度为60℃,反应时间为30min,剂油比为1：15,在反应进行到25min时加入相转移催化剂脱硫率达最大,油脱硫率可达90.0%。     

超声辅助的柴油催化氧化脱硫研究

在超声作用下采用[(C16H31)N(CH3)3]3[PW12040]催化剂将柴油中的含硫有机物(主要为二苯并噻吩类)氧化成相应的砜,用 N,N-二甲基甲酰胺(DMF)作萃取剂将砜从柴油中萃取除去.考察了[(C16H31)N(CH3)3]3[PW12040]的量、超声条件(频率、声强)、温度等因素对柴油脱硫的影响.