不同脱硫剂脱除煤中硫的研究

在不同的条件下,考察了不同脱硫剂对煤中全硫和各形态硫的脱硫效果.结果发现,次氯酸钠和双氧水等氧化类脱硫剂对煤中无机硫的脱除效果明显,而甲醇和N,N-二甲基乙醇胺等萃取类脱硫剂对煤中有机硫的脱除效果较好;此两类脱硫剂具有协同效应,配合使用可以增强煤中硫的脱除效果;另外,超声波和微波的辐照作用可以增强有机硫的脱除效率.     

负载型Ce、La催化氧化脱除柴油中有机硫化物

Ce基催化剂因其具有较强的储放氧功能,在催化氧化反应中有着广泛的应用。而其用于催化氧化脱除柴油中有机硫化物的研究,并未有报道。本文用负载法制备Ce、La高丰度稀土元素的催化剂,用于催化分子氧氧化脱除柴油中硫化物,旨在分析其催化氧化效果。结果表明:反应温度越高其催化氧化活性越大,柴油脱硫率最高达70%以上。     

杂多酸季铵盐催化氧化脱除柴油中硫化物的研究

随着国内燃料油标准日益严格,催化氧化脱硫技术被使用于柴油深度脱硫研究。实验合成新型杂多酸季铵盐催化剂,催化脱除柴油中硫化物的研究,实验中使用单因素对脱硫工艺进行优化,得出:使用[BMIM]2[CTMA]PMo12O40催化剂,在(n(C)/n(S)=0.06、n(H2O2)/n(S)=5、T=60℃、t=40 min、萃取剂(乙腈)=5 mL)反应条件下,柴油的脱硫率高达93.1%,硫含量从原来的369μg/g降至25.5μg/g。     

高硫原油中硫化物的脱除工艺及脱硫剂

负载型过渡金属磷化物馏分油深度加氢脱硫催化剂制备方法属于新材料、石油炼制和石油化工技术领域。是采用一种新型的载体材料担载金属活性组分，并用一种新的活化方法合成表面金属磷化物，制备石油炼制工业中所用汽油、煤油、柴油、蜡油等馏分油深度加氢脱硫催化剂的方法，新型载体材料是指由中孔分子筛与多孔氧化物构成的复合载体，该方法制备出了高活性的加氢脱硫催化剂。有益效果是，可将石油馏分油中最难脱除的二苯并噻吩及其衍生物几乎全部转化。主要用于制造炼油加氢精制催化剂和石油化工生产中原料预精制加氢脱硫催化剂。     

氧化萃取法脱除焦化柴油中硫氮化合物

以过氧化氢为氧化剂,磷钨酸为催化剂,四乙基溴化铵为相转移催化剂,糠醛为萃取剂,采用催化氧化反应与溶剂萃取相结合的试验方法对焦化柴油进行硫氮脱除反应,并对工艺条件进行优化。结果表明,以50 mL焦化柴油为基础,在H2O2体积为7 mL、磷钨酸用量为0.28 g/L、四乙基溴化铵质量为0.10 g、反应温度60℃、氧化反应70 min、25 mL糠醛萃取三次的最优工艺条件下,柴油中硫质量分数由647μg/g降至62.58μg/g,脱硫率达90.33%;而氮质量分数由775.26μg/g降至29.85μg/g,脱氮率高达96.15%。氧化溶液与萃取剂回收后经处理均可重复利用。     

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。     

高硫柴油吸附脱硫剂的研究

研究了不同的Cu2+分子筛在常温常压下吸附高硫柴油中的硫化合物。采用水热合成法和离子交换法制备含Cu2+分子筛(CuMCM41和CuZSM5),用于固定床吸附脱硫。其中每克CuMCM41处理5 mL高硫柴油后达到饱和,并且能把含硫量降到300×10-6(质量分数)。吸附剂对硫化物具有很强的选择性,用CuMCM41来吸附模拟柴油,吸附结果表明它对噻吩和苯并噻吩的吸附性比对萘要强。     

活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性

研究了活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性。采用气相色谱-硫化学发光检测器（GC-SCD）分析了汽油和柴油中噻吩类硫化物的分布及浓度;以活性炭作为催化剂,以30％过氧化氢溶液为氧化剂,在甲酸存在条件下考察了汽油和柴油中噻吩类硫化物催化氧化脱除的选择性,讨论了硫化物中硫原子电子密度对硫化物氧化选择性的影响。结果表明：汽油中噻吩类硫化物主要有噻吩（T）及其烷基衍生物（T alkylated derivatives）和苯并噻吩（BT）;而柴油中噻吩类硫化物主要分布有苯并噻吩(BT)及其烷基衍生物(BT alkylated derivatives)和二苯并噻吩（DBT）及其烷基衍生物（DBT alkylated derivatives）;硫原子电子密度大于5.716的含3个C烷基噻吩（C3-T）、BT、BT alkylated derivatives、DBT 和DBT alkylated derivatives 能被催化氧化脱除,硫原子的电子密度越大,其被氧化的速率越快,被脱除的选择性也越大;被脱除选择性顺序为：DBT alkylated derivatives > DBT > BT alkylated derivatives> BT> C3-T;然而硫原子电子密度小于5.716的T,含1个烷基噻吩（C1-T）和含2个C烷基噻吩（C2-T）则不能被氧化脱除。采用此方法,能将初始硫浓度为1200 μg•g^-1的柴油降低至小于10 μg•g^-1,可将初始硫浓度为320 μg•g^-1的汽油降低至155 μg•g^-1。     

直馏高硫柴油选择性催化氧化-萃取脱硫研究

对委内瑞拉直馏高硫柴油进行了氧化-萃取脱硫工艺的实验室研究。结果表明,采用H2O2-H3PO4·12WO3氧化反应体系,柴油与H2O2的体积比为2：1,H3PO4·12WO3用量在0．02g/mL以上,十六烷基三甲基溴化铵加入量为0．002g／mL,反应温度为60℃,反应时间30min,用DMF进行3级萃取,剂油比体积比为1：2,脱硫后的柴油中硫的质量分数在0．16％以下,柴油收率为69％-72％,双氧水重复利用4次以上。萃取液中的富硫油可以全部回收．     

干法脱硫中EF-2型精脱硫剂硫容技术探讨

介绍EF－2型精脱硫剂在兖矿鲁南化肥厂甲醇净化工段干法脱硫工序中的使用及总硫指标变化情况，对出现的问题进行分析探讨，提出改造措施，并对改造前后的效果进行了对比。     

出口柴油硫含量在馏分中分布研究

采用紫外荧光法对切割后柴油各窄馏分油进行了硫含量的测定。结果表明:轻馏分段中含量占整个馏分中硫质量分数相对较小,重馏分段所占比例相对很大,80%~100%窄馏分中硫质量分数占整个馏分中硫质量分数的32.538%~34.807%,是0%~20%窄馏分段中硫质量分数的3倍,说明硫含量主要集中在重馏分段中。     

Sulfur Removal from Low‐Sulfur Gasoline and Diesel Fuel by Metal‐Organic Frameworks

Several materials in the class of metal‐organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low‐sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total‐sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low‐sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper‐containing MOF (copper benzene‐1,3,5‐tricarboxylate, Cu‐BTC‐MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT‐based model oils. Moreover, the sulfur content of low‐sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time‐resolved measurements demonstrated that the sulfur‐sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis‐systems or exhaust gas sensors.     

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.     

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.     

复合固硫剂的实验室脱硫试验

介绍了提高钙基利用率的方法，通过掺混和调质的大量实验室试验制得了在高温下脱硫率较高的复合固硫剂，取得了良好的效果。同时，对所研制的复合固硫剂物理特性通过压汞试验进行了定性分析。     

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。     

超声与非超声条件下柴油氧化脱硫的对比研究

通过氧化反应与溶剂萃取分离相结合的方法对催化裂化柴油氧化脱硫。在催化氧化溶剂抽提的基础上,同时又用功率超声作用于该过程,开辟了一条全新的柴油氧化脱硫技术。考察氧化剂油比、氧化剂与催化剂的体积比、氧化温度、反应时间等因素对脱硫效果的影响。实验结果表明：在超声频率为28kHz作用下,以H2O2为氧化剂,甲酸为催化剂,萃取剂为DMF,萃取剂油比（体积比）为1：1,一次萃取20min,萃取次数为2次时氧化剂油比（体积比）为1：10,H2O2：甲酸体积比为1：1,氧化温度为50℃,反应时间为10min为最佳,其脱硫率达到93.2%。     

Sulfur removal from hydrotreated petroleum fractions using ultrasound-assisted oxidative desulfurization process

Ultrasound-assisted oxidative desulfurization (UAOD) process was applied to diesel oil and petroleum product feedstock containing model sulfur compounds (benzothiophene, dibenzothiophene and dimethyldibenzothiophene). The influence of oxidant amount, volume of solvent for the extraction step and time and temperature of ultrasound treatment (20 kHz, 750 W, operating at 40%) was investigated. Using the optimized conditions for UAOD, sulfur removal up to 99% was achieved for model compounds in petroleum product feedstock using a molar proportion for H₂O₂:acetic acid:sulfur of 64:300:1, after 9 min of ultrasound treatment at 90 °C, followed by extraction with methanol (optimized solvent and oil ratio of 0.36). Using the same reagent amount and 9 min of ultrasound the removal of sulfur was higher than 75% for diesel oil samples. Sulfur removal without ultrasound using the same conditions was lower than 82% for model compounds and 55% for diesel oil samples showing that ultrasound improved the efficiency of oxidative desulfurization. In comparison to conventional hydrodesulfurization, the proposed UAOD process can be performed under relatively mild conditions (atmospheric pressure and 90 °C, without using metallic catalysts).     

Fast Oxidative Removal of Refractory Aromatic Sulfur Compounds by a Magnetic Ionic Liquid

Magnetic ionic liquids (MIL) are extensively used in extraction and catalytic processes. Here, a series of MIL, i.e., 1‐n‐butyric acid‐3‐methylimidazolium chloride/xFeCl₃ ([C₃H₆COOHmim]Cl/xFeCl₃; x = 0.5, 1, 1.5, 2), were synthesized and characterized by infrared spectroscopy, visible absorption spectrometry, and electrospray ionization mass spectrometry. The MIL [C₃H₆COOHmim]Cl/2FeCl₃ was found to be highly active for the extraction and catalytic oxidative desulfurization of a model oil under mild conditions. Of note, the removal of benzothiophene, which has been regarded as a refractory aromatic sulfur compound, could be achieved at up to 100 % in 10 min. After reaction, the MIL could be easily separated from the model oil by applying an external magnetic field, due to its paramagnetic properties.